Ethylene interpolymer products having intermediate branching

ABSTRACT

This disclosure relates to ethylene interpolymer product having intermediate branching. Intermediate branching was defined as branching that was longer than the branch length due to comonomer and shorter than the entanglement molecular weight (Me). Intermediately branched ethylene interpolymer products were produced in a continuous solution polymerization process employing an intermediate branching catalyst formulation. Intermediately branched ethylene interpolymer products were characterized by a Non-Comonomer Index Distribution (NCIDi), a melt index from 0.3 to 500 dg/minute, a density from 0.858 to 0.965 g/cm3, a polydispersity (Mw/Mn) from about 2 to about 25 and a CDBI50 from about 10% to about 98%. A method based on triple detection cross fractionation chromatography (3D-CFC) was disclosed to measure NCIDi.

TECHNICAL FIELD

This disclosure relates to: copolymers of ethylene and α-olefins havingintermediate branching; continuous polymerization processes tomanufacture such copolymers; analytical methods to characterize suchcopolymers; and the utility of such copolymers in a myriad ofmanufactured articles.

BACKGROUND

The polymer industry is in constant need of improved ethyleneinterpolymer products, e.g. in flexible film applications such as foodpackaging, shrink films and stretch films. As disclosed hereinafter,ethylene interpolymer products having intermediate branching haveperformance attributes that are advantageous in film applications.Relative to competitive ethylene interpolymer products of similardensity and melt index, films produced from intermediately branchedethylene interpolymer products have, for example, higher dart impact,higher tensile strength and/or improved optical properties, such ashigher film 45° gloss and lower film haze. The polymer industry is alsoin need of improved ethylene interpolymer products for rigidapplications, including, but not limited to containers, lids, caps andtoys, etc. Ethylene interpolymer products having intermediate branchingalso have utility in such rigid applications. Ethylene interpolymerproducts having intermediate branching were produced in a continuoussolution polymerization process. Solution polymerization processes aretypically carried out at temperatures above the melting point of theethylene interpolymer being synthesized. In a typical solutionpolymerization process, catalyst components, solvent, monomer(s) andhydrogen are fed under pressure to one or more reactors. A wide varietyof vessels (e.g. polymerization reactors, etc.) and vessel arrangementscan be used under a wide range of process conditions allowing theproduction of a wide variety of ethylene interpolymer products. Postreactor, the polymerization reaction is typically quenched by adding acatalyst deactivator and passivated by adding an acid scavenger. Oncepassivated, the polymer solution is forwarded to polymer recoveryoperations where the ethylene interpolymer product is separated fromprocess solvent, unreacted residual ethylene and unreacted optionalα-olefin(s).

SUMMARY OF DISCLOSURE

In this application, ethylene interpolymer products having intermediatebranching are disclosed, as well as a process to manufacture suchproducts and a method to measure the Non-Comonomer Index Distribution(NCID_(i)) to quantify the amount of intermediate branching in suchproducts. Intermediate branching was defined as branching that waslonger than the branch length due to comonomer (e.g. C₄ or C₆ branchesfrom 1-hexene or 1-octene comonomers, respectively) and shorter than theentanglement molecular weight, M_(e) (M_(e) is a well-known concept inpolymer physics). The amount of intermediate branching in the disclosedethylene interpolymer products was characterized by the ‘Non-ComonomerIndex (NCI)’, as well as the ‘Non-Comonomer Index Distribution(NCID_(i)), which was generated using triple detection crossfractionation chromatography (3D-CFC) techniques. Ethylene interpolymerproducts, having intermediate branching, may, or may not contain longchain branching as characterized by the Long Chain Branching Factor(LCBF).

Long chain branches were branches that were greater than or equal toM_(e); long chain branches were macromolecular in nature and wereevident in rheological measurements. The advantages of ethyleneinterpolymer products having intermediate branching in filmsapplications is disclosed and compared with comparative ethyleneinterpolymer product films that did not contain intermediate branching.

The following embodiments are provided for the purpose of a specificdisclosure for the appended claims.

One embodiment of this disclosure, hereinafter embodiment [1], is fullydescribed immediately below.

-   -   [I]-1. An ethylene interpolymer product comprising:        -   (i) a first ethylene interpolymer;        -   (ii) a second ethylene interpolymer, and;        -   (iii) optionally a third ethylene interpolymer;        -   wherein said second ethylene interpolymer is characterized            by an intermediate branching, wherein said intermediate            branching is characterized by a Non-Comonomer Index            Distribution, NCID_(i), having a value characterized by Eq.            (1a) and Eq. (1b);

NCID_(i)≤1.000−0.00201(log M _(i)−log M _(o)+4.93)+0.00137(log M_(i)−log M _(o)+4.93)²−0.00034(log M _(i)−log M _(o)+4.93)³   Eq.(1a)

NCID_(i)≥0.730−0.00388(log M _(i)−log M _(o)+4.93)+0.00313(log M_(i)−log M _(o)+4.93)²−0.00069(log M _(i)−log M _(o)+4.93)³  Eq.(1b)

-   -   -   wherein, M_(o) is a peak molecular weight that characterizes            a molecular weight distribution of said second ethylene            interpolymer when fit to a log normal distribution;        -   wherein a first derivative of said NCID_(i)

$\frac{{dNCID}_{i}}{d\log M_{i}},$

-   -   -    Eq. (2);

$\begin{matrix}{\frac{{dNCID}_{i}}{d\log M_{i}} = {\beta_{1} + {2{\beta_{2}\left( {{\log M_{i}} - {\log M_{o}} + 4.93} \right)}} + {3{\beta_{3}\left( {{\log M_{i}} - {\log M_{o}} + 4.93} \right)}^{2}}}} & {{Eq}.(2)}\end{matrix}$

-   -   -   has a value of ≤−0.0001, coefficients β₀, β₁, β₂ and β₃ are            generated by fitting said NCID_(i) of said second ethylene            interpolymer to a third order polynomial, Eq. (3),

NCID_(i)=β₀+β₁(log M _(i)−log M _(o)+4.93)+β₂(log M _(i)−log M_(o)+4.93)²+β₃(log M _(i)−log M _(o)+4.93)³  Eq.(3)

-   -   -   wherein said NCID_(i) may be experimentally measured or            computer simulated;

    -   wherein said ethylene interpolymer product does not contain long        chain branching as characterized by a dimensionless Long Chain        Branching Factor, LCBF, having a value of <0.001.

    -   [I]-2. The ethylene interpolymer as described in [I]-1, wherein        said first ethylene interpolymer is synthesized using a        homogenous catalyst formulation and said second ethylene        interpolymer is synthesized using an intermediate branching        catalyst formulation.

    -   [I]-3. The ethylene interpolymer product as described in [I]-2,        wherein said homogeneous catalyst formulation is an unbridged        single site catalyst formulation and said intermediate branching        catalyst formulation is an in-line intermediate branching        catalyst formulation or a batch intermediate branching catalyst        formulation.

    -   [I]-4. The ethylene interpolymer product as described in [I]-1        having a melt index from about 0.3 to about 500 dg/minute and a        density from about 0.858 to about 0.965 g/cc; wherein melt index        is measured according to ASTM D1238 (2.16 kg load and 190° C.)        and density is measured according to ASTM D792.

    -   [I]-5. The ethylene interpolymer product as described in [I]-1        having a M_(w)/M_(n) from about 2 to about 25.

    -   [I]-6. The ethylene interpolymer product as described in [I]-1        having a CDBI₅₀ from about 10% to about 98%.

    -   [I]-7. The ethylene interpolymer product as described in [I]-1;        wherein        -   (i) said first ethylene interpolymer has a melt index from            about 0.001 to about 1000 dg/minute, a density from about            0.855 g/cm³ to about 0.975 g/cc and is from about 0 to 60            weight percent of said ethylene interpolymer product;        -   (ii) said second ethylene interpolymer has melt index from            about 0.001 to about 1000 dg/minute, a density from about            0.89 g/cm³ to about 0.965 g/cc and is from about 10 to 99            weight percent of said ethylene interpolymer product;        -   (iii) optionally said third ethylene interpolymer has a melt            index from about 0.1 to about 10000 dg/minute, a density            from about 0.855 to about 0.975 g/cc and is from 0 to about            30 weight percent of said ethylene interpolymer product;        -   wherein melt index is measured according to ASTM D1238 (2.16            kg load and 190° C.), density is measured according to ASTM            D792 and weight percent is the weight of said first, said            second or said optional third ethylene interpolymer divided            by the weight of said ethylene interpolymer product.

    -   [I]-8. The ethylene interpolymer product as described in [I]-1        synthesized using a solution polymerization process.

    -   [I]-9. The ethylene interpolymer product as described in [I]-1        further comprising from 0.001 to about 10 mole percent of one or        more α-olefin.

    -   [I]-10. The ethylene interpolymer product as described in [I]-9;        wherein said one or more α-olefin are C₃ to C₁₀ α-olefins.

    -   [I]-11. The ethylene interpolymer product as described in        [I]-10; wherein said one or more α-olefin is 1-hexene, 1-octene        or a mixture of 1-hexene and 1-octene.

    -   [I]-12. The ethylene interpolymer product as described in [I]-1        wherein said third ethylene interpolymer is synthesized using a        heterogeneous catalyst formulation or a homogeneous catalyst        formulation or an intermediate branching catalyst formulation.

    -   [I]-13. The ethylene interpolymer product as described in [I]-1;        wherein said first ethylene interpolymer has a first CDBI₅₀ from        about 20 to about 98%, said second ethylene interpolymer has a        second CDBI₅₀ from about 20 to about 70% and said optional third        ethylene interpolymer has a third CDBI₅₀ from about 20 to about        98%.

    -   [I]-14. The ethylene interpolymer product as described in        [I]-13; wherein said first CDBI₅₀ is higher than said second        CDBI₅₀.

Another embodiment of this disclosure, hereinafter embodiment [II], isfully described immediately below.

-   -   [II]-1. An ethylene interpolymer product comprising:        -   (i) a first ethylene interpolymer;        -   (ii) a second ethylene interpolymer, and;        -   (iii) optionally a third ethylene interpolymer;        -   wherein said second ethylene interpolymer is characterized            by an intermediate branching, wherein said intermediate            branching is characterized by a Non-Comonomer Index            Distribution, NCID, having a value characterized by Eq. (1a)            and Eq. (1b), wherein, M_(o) is a peak molecular weight that            characterizes a molecular weight distribution of said second            ethylene interpolymer when fit to a log normal distribution;        -   wherein a first derivative of said NCID_(i),

$\frac{{dNCID}_{i}}{d\log M_{i}},$

-   -   -    Eq. (2), has a value of ≤−0.0001, coefficients β₀, β₁, β₂            and β₃ are generated by fitting said NCID_(i) of said second            ethylene interpolymer to a third order polynomial, Eq. (3),        -   wherein said NCID_(i) may be experimentally measured or            computer simulated;        -   wherein said ethylene interpolymer product contains long            chain branching as characterized by a dimensionless Long            Chain Branching Factor, LCBF, having a value ≥0.001.

    -   [II]-2. The ethylene interpolymer as described in [II]-1,        wherein said first ethylene interpolymer is synthesized using a        homogenous catalyst formulation and said second ethylene        interpolymer is synthesized using an intermediate branching        catalyst formulation. [II]-3. The ethylene interpolymer product        as described in [II]-2, wherein said homogeneous catalyst        formulation is a bridged single site catalyst formulation and        said intermediate branching catalyst formulation is an in-line        intermediate branching catalyst formulation or a batch        intermediate branching catalyst formulation. [II]-4. The        ethylene interpolymer product as described in [II]-1 having a        melt index from about 0.3 to about 500 dg/minute and a density        from about 0.858 to about 0.965 g/cc; wherein melt index is        measured according to ASTM D1238 (2.16 kg load and 190° C.) and        density is measured according to ASTM D792.

    -   [II]-5. The ethylene interpolymer product as described in [II]-1        having a M_(w)/M_(n) from about 2 to about 25.

    -   [II]-6. The ethylene interpolymer product as described in [II]-1        having a CDBI₅₀ from about 10% to about 98%.

    -   [II]-7. The ethylene interpolymer product as described in        [II]-1; wherein        -   (i) said first ethylene interpolymer has a melt index from            about 0.001 to about 1000 dg/minute, a density from about            0.855 g/cm³ to about 0.975 g/cc and is from about 0 to 60            weight percent of said ethylene interpolymer product;        -   (ii) said second ethylene interpolymer has melt index from            about 0.001 to about 1000 dg/minute, a density from about            0.89 g/cm³ to about 0.965 g/cc and is from about to 99            weight percent of said ethylene interpolymer product;        -   (iii) optionally said third ethylene interpolymer has a melt            index from about 0.1 to about 10000 dg/minute, a density            from about 0.855 to about 0.975 g/cc and is from 0 to about            30 weight percent of said ethylene interpolymer product;        -   wherein melt index is measured according to ASTM D1238 (2.16            kg load and 190° C.), density is measured according to ASTM            D792 and weight percent is the weight of said first, said            second or said optional third ethylene interpolymer divided            by the weight of said ethylene interpolymer product.

    -   [II]-8. The ethylene interpolymer product as described in [II]-1        synthesized using a solution polymerization process.

    -   [II]-9. The ethylene interpolymer product as described in [II]-1        further comprising from 0.001 to about 10 mole percent of one or        more α-olefin.

    -   [II]-10. The ethylene interpolymer product as described in        [II]-9; wherein said one or more α-olefin are C₃ to C₁₀        α-olefins.

    -   [II]-11. The ethylene interpolymer product as described in        [II]-10; wherein said one or more α-olefin is 1-hexene, 1-octene        or a mixture of 1-hexene and 1-octene.

    -   [II]-12. The ethylene interpolymer product as described in        [II]-1 wherein said third ethylene interpolymer is synthesized        using a heterogeneous catalyst formulation or a homogeneous        catalyst formulation or an intermediate branching catalyst        formulation.

    -   [II]-13. The ethylene interpolymer product as described in        [II]-1; wherein said first ethylene interpolymer has a first        CDBI₅₀ from about 20 to about 98%, said second ethylene        interpolymer has a second CDBI₅₀ from about 20 to about 70% and        said optional third ethylene interpolymer has a third CDBI₅₀        from about 20 to about 98%.

    -   [II]-14. The ethylene interpolymer product as described in        [II]-13; wherein said first CDBI₅₀ is higher than said second        CDBI₅₀.

An additional embodiment of this disclosure, hereinafter embodiment[III], is fully described immediately below.

-   -   [III]-1. An ethylene interpolymer product comprising at least        one ethylene interpolymer; wherein said ethylene interpolymer is        characterized by:        -   an intermediate branching wherein said intermediate            branching is characterized by a Non-Comonomer Index            Distribution, NCID, having a value characterized by Eq. (1a)            and Eq. (1b);        -   wherein, M_(o) is a peak molecular weight that characterizes            a molecular weight distribution of said ethylene            interpolymer when fit to a log normal distribution;        -   wherein a first derivative of said NCID_(i),

$\frac{{dNCID}_{i}}{d\log M_{i}},$

-   -   -    Eq. (2), has a value of ≤−0.0001, coefficients so, β₁, β₂            and β₃ are generated by fitting said NCID_(i) of said            ethylene interpolymer to a third order polynomial, Eq. (3),            wherein said NCID_(i) may be experimentally measured or            computer simulated.

    -   [III]-2. The ethylene interpolymer product as described in        [III]-1, wherein said ethylene interpolymer is synthesized using        an intermediate branching catalyst formulation.

    -   [III]-3. The ethylene interpolymer product as described in        [III]-2, wherein said intermediate branching catalyst        formulation is an in-line intermediate branching catalyst        formulation or a batch intermediate catalyst formulation.

    -   [III]-4. The ethylene interpolymer product as described in        [III]-1, comprising a first ethylene interpolymer, a second        ethylene interpolymer and optionally a third ethylene        interpolymer;        -   wherein at least one of said first, said second and/or said            third ethylene interpolymer is characterized by said            NCID_(i) having a value characterized by Eq. (1a) and Eq.            (1b) and said first derivative Eq. (2) has a value ≤−0.0001,            wherein said NCID_(i) may be experimentally measured or            computer simulated.

    -   [III]-5. The ethylene interpolymer product as described in        [III]-4, wherein said first ethylene interpolymer is synthesized        with a first heterogeneous catalyst formulation, said second        ethylene interpolymer is synthesized with a second heterogeneous        catalyst formulation and said optional third ethylene        interpolymer is synthesized with a third heterogeneous catalyst        formulation; wherein said first, said second and said third        heterogeneous catalyst formulations may be the same formulation        or different formulations with the proviso that at least one of        said first, said second and said third heterogeneous catalyst        formulations is an intermediate branching catalyst formulation.

    -   [III]-6. The ethylene interpolymer product as described in        [III]-1, further characterized by a dimensionless Long Chain        Branching Factor, LCBF, having a value <0.001.

    -   [III]-7. The ethylene interpolymer product as described in        [III]-1 having a melt index from about 0.3 to about 500        dg/minute and a density from about 0.890 to about 0.965 g/cc;        wherein melt index is measured according to ASTM D1238 (2.16 kg        load and 190° C.) and density is measured according to ASTM        D792.

    -   [III]-8. The ethylene interpolymer product as described in        [III]-1 having a M_(w)/M_(n) from about 2.2 to about 25.

    -   [III]-9. The ethylene interpolymer product as described in        [III]-1 having a CDBI₅₀ from about 10% to about 98%.

    -   [III]-10. The ethylene interpolymer product as described in        [III]-5; wherein        -   (i) said first ethylene interpolymer has a melt index from            about 0.001 to about 1000 dg/minute, a density from about            0.890 g/cm³ to about 0.965 g/cc and is from about 0 to 60            weight percent of said ethylene interpolymer product;        -   (ii) said second ethylene interpolymer has melt index from            about 0.001 to about 1000 dg/minute, a density from about            0.89 g/cm³ to about 0.965 g/cc and is from about 10 to 99            weight percent of said ethylene interpolymer product; and        -   (iii) optionally said third ethylene interpolymer has a melt            index from about 0.1 to about 10000 dg/minute, a density            from about 0.89 to about 0.965 g/cc and is from 0 to about            30 weight percent of said ethylene interpolymer product;

    -   wherein melt index is measured according to ASTM D1238 (2.16 kg        load and 190° C.), density is measured according to ASTM D792        and weight percent is the weight of said first, said second or        said optional third ethylene interpolymer divided by the weight        of said ethylene interpolymer product.

    -   [III]-11. The ethylene interpolymer product as described in        [III]-1 synthesized using a solution polymerization process.

    -   [III]-12. The ethylene interpolymer product as described in        [III]-1 further comprising from 0.001 to about 10 mole percent        of one or more α-olefin.

    -   [III]-13. The ethylene interpolymer product as described in        [III]-11; wherein said one or more α-olefin are C₃ to C₁₀        α-olefins.

    -   [III]-14. The ethylene interpolymer product as described in        [III]-12; wherein said one or more α-olefin is 1-hexene,        1-octene or a mixture of 1-hexene and 1-octene.

One embodiment of this disclosure, hereinafter embodiment [IV], relatesto a method to determine NCID_(i), as fully described immediately below.

-   -   [IV]-1. A method to determine the Non-Comonomer Index        Distribution, NCDI_(i), of an ethylene interpolymer product,        comprising:        -   a) placing from about 150 to about 300 mg of said ethylene            interpolymer product into a sample dissolution vessel of a            Polymer Char Crystaf-TREF unit;        -   b) dissolving said ethylene interpolymer product by adding            35 mL of solvent to said dissolution vessel, heating said            vessel to 140° C., then stirring for about 2 to about 3            hours to form a polymer solution; wherein said solvent is            1,2,4-trichlorobenzene containing 250 ppm of            2,6-di-tert-butyl-4-methylphenol;        -   c) transferring said polymer solution to a TREF column and            equilibrating said TREF column at 110° C. for about 20 to            about 45 minutes;        -   d) cooling said polymer solution by reducing the temperature            of said TREF column to 30° C., employing a cooling rate of            0.2° C./minute, to form a crystallized ethylene interpolymer            product and equilibrating said TREF column at 30° C. for 90            minutes;        -   e) heating said TREF column to a first dissolution            temperature, employing a heating rate of 1.0° C./min, and            maintaining said TREF column at said first dissolution            temperature for at least 50 minutes;        -   f) eluting a first TREF fraction from said TREF column using            said solvent flowing at 1 mL/minute;        -   g) transferring said first TREF fraction through a heated            transfer line into a Size Exclusion Chromatography (SEC)            unit operating at 140° C. to produce an SEC effluent;            wherein said heated transfer line is maintained at 140° C.;        -   h) passing said SEC effluent through a SEC detection system;            wherein said SEC detection system includes a differential            refractive index detector (DRI) to determine a polymer            concentration; a dual-angle (15° and 90°) light scattering            detector to determine a viscosity average molecular weight,            M_(v) ^(f); and, a differential viscometer to determine an            intrinsic viscosity, [η]^(f), of said first TREF fraction;            wherein superscript f represents the f^(th) TREF fraction,            where f=1 for said first TREF fraction;        -   i) calculating a Non-Comonomer Index, NCI^(f), of said first            TREF fraction according to Eq. (4);

$\begin{matrix}{{NCI}^{f} = \frac{1000000\left( {\lbrack\eta\rbrack^{f}/\left( M_{v}^{f} \right)^{0.725}} \right)}{\left( {391.98 - {{Ax}\left( {{B \times T^{f}} + C} \right)}} \right.}} & {{Eq}.(4)}\end{matrix}$

-   -   -   wherein, A, B and C are constants that depend on the            α-olefin comonomer in said ethylene interpolymer and T^(f)            is a weight average TREF elution temperature of said first            TREF fraction calculated based on the re-constructed            analytical TREF profile of said ethylene interpolymer            product;        -   j) incrementally increasing the temperature of said TREF            column and repeat steps (e) through (i), such that said            ethylene interpolymer is fractionated into at least 5 TREF            fractions to less than 21 TREF fractions;        -   k) calculating said Non-Comonomer Index Distribution            (NCID_(i)) of said ethylene interpolymer according to Eq.            (5)

NCID_(i)=Σ₁ ^(f)(wt.fr.)^(f)(w _(i) log(M _(i)))^(f)×NCI^(f)  Eq.(5)

-   -   -   wherein (wt.fr.)^(f) represents the weight fraction of the            f^(th) TREF fraction and (w_(i) log(M_(i)))^(f) represents            the weight fraction of the f^(th) TREF fraction having molar            mass M_(i) and superscript f represents the TREF fraction            number.

    -   [IV]-2. The method as described in [IV]-1; wherein said Polymer        Char Crystaf-TREF unit was programmed and controlled with        Polymer Char TREF software having step-elution capability.

    -   [IV]-3. The method as described in [IV]-1; wherein said Size        Exclusion Chromatography (SEC) unit comprised a PL 220        high-temperature chromatography unit equipped with either four        Shodex columns (HT803, HT804, HT805 and HT806), or four PL Mixed        ALS or BLS columns; and SEC data was acquired and processed        using Cirrus GPC software and Excel spreadsheet to calculate        said absolute molar mass and said intrinsic viscosity.

    -   [IV]-4. The method as described in [IV]-1, wherein said constant        A is 2.1626, said constant B is −0.6737 and said C is 63.6727,        when the α-olefin is 1-octene.

An additional embodiment of this disclosure, hereinafter embodiment [V],relates to the manufacture an ethylene interpolymer product havingintermediate branching, as fully described immediately below.

-   -   [V]-1. A continuous solution polymerization process wherein an        ethylene interpolymer product is produced, wherein said ethylene        interpolymer product is characterized as having an intermediate        branching, wherein said intermediate branching is characterized        by a Non-Comonomer Index Distribution, NCID_(i), comprising:        -   a) injecting ethylene, a process solvent, a first catalyst            formulation, one or more α-olefins and optionally hydrogen            into a first reactor to produce a first exit stream            containing a first ethylene interpolymer in said process            solvent;        -   b) passing said first exit stream into a second reactor and            injecting into said second reactor, ethylene, said process            solvent, an intermediate branching catalyst formulation, one            or more α-olefins and optionally hydrogen to produce a            second exit stream containing a second ethylene interpolymer            and said first ethylene interpolymer in said process            solvent;        -   c) optionally adding a catalyst deactivator A to said second            exit stream, downstream of said second reactor, forming a            deactivated solution A;        -   d) passing said second exit stream, or optionally said            deactivated solution A, into a third reactor and optionally            injecting into said third reactor, ethylene, process            solvent, one or more α-olefins, hydrogen and a third            catalyst formulation to produce a third exit stream            containing an optional third ethylene interpolymer, said            second ethylene interpolymer and said first ethylene            interpolymer in said process solvent;        -   e) adding a catalyst deactivator B to said third exit            stream, downstream of said third reactor, forming a            deactivated solution B; with the proviso that e) is skipped            if said catalyst deactivator A was added in c);        -   optionally, b) through e) are skipped and replaced with f)            through j), with the proviso that if b) through e) are not            skipped, e) is followed by k);        -   f) injecting ethylene, said process solvent, an intermediate            branching catalyst formulation, one or more α-olefins and            optionally hydrogen into a second reactor to produce a            second exit stream containing a second ethylene interpolymer            in said process solvent;        -   g) combining said first and said second exit streams,            downstream of said second reactor, to form a third exit            stream;        -   h) optionally adding a catalyst deactivator A to said third            exit stream forming a deactivated solution A;        -   i) passing said third exit stream into a third reactor and            optionally injecting into said third reactor, ethylene, said            process solvent, one or more α-olefins, hydrogen and a third            catalyst formulation to produce a fourth exit stream            containing an optional third ethylene interpolymer, said            second ethylene interpolymer and said first ethylene            interpolymer in said process solvent;        -   j) adding a catalyst deactivator B to said fourth exit            stream, downstream of said third reactor, forming a            deactivated solution B; with the proviso that j) is skipped            if said catalyst deactivator A was added in h);        -   k) adding a passivator to said deactivated solution A or            said deactivated solution B to form a passivated solution;        -   l) phase separating said passivated solution to recover said            ethylene interpolymer product;        -   wherein said ethylene interpolymer product is characterized            by said Non-Comonomer Index Distribution, NCID_(i), having a            value characterized by Eq. (1a) and Eq. (1b);        -   wherein, M_(o) is a peak molecular weight that characterizes            a molecular weight distribution of said second ethylene            interpolymer when fit to a log normal distribution;        -   wherein a first derivative of said NCID_(i),

$\frac{{dNCID}_{i}}{d\log M_{i}},$

-   -   -    Eq. (2), has a value of ≤−0.0001, coefficients β₀, β₁, β₂            and β₃ are generated by fitting said NCID_(i) of said second            ethylene interpolymer to a third order polynomial, Eq. (3),            wherein said NCID_(i) may be experimentally measured or            computer simulated.

    -   [V]-2. The process as described in [V]-1, wherein said first        catalyst formulation is an unbridged single site catalyst        formulation; wherein said ethylene interpolymer product is        further characterized by a dimensionless Long Chain Branching        Factor, LCBF, having a value <0.001.

    -   [V]-3. The process as described in [V]-1, wherein said first        catalyst formulation is a bridged metallocene catalyst        formulation; wherein said ethylene interpolymer product is        further characterized by a dimensionless Long Chain Branching        Factor, LCBF, having a value ≥0.001.

    -   [V]-4. The process as described in [V]-1, wherein said first        catalyst formulation is said intermediate branching catalyst        formulation, or a second intermediate branching formulation, or        a Ziegler-Natta catalyst formulation.

    -   [V]-5. The process as described in [V]-1, wherein said third        catalyst formulation is one or more of: an unbridged single site        catalyst formulation; a bridged metallocene catalyst        formulation; said intermediate branching catalyst formulation; a        second intermediate branching catalyst formulation; a        Ziegler-Natta catalyst formulation.

    -   [V]-6. The process as described in [V]-1, wherein said ethylene,        said one or more α-olefin, said hydrogen and said first catalyst        formulation are not injected into said first reactor and said        first ethylene interpolymer is not formed; optionally, said        process solvent is not injected into said first reactor.

    -   [V]-7. The process as described in [V]-1, wherein said        intermediate branching catalyst formulation is an in-line        intermediate branching catalyst formulation formed in an in-line        process comprising:        -   a) forming a first product mixture in a first heterogeneous            catalyst assembly by combining a stream S1 and a stream S2            and allowing said first product mixture to equilibrate for a            HUT-1 seconds; wherein said stream S1 comprises a magnesium            compound and an aluminum alkyl in said process solvent and            said stream S2 comprises a chloride compound in said process            solvent;        -   b) forming a second product mixture in said first            heterogeneous catalyst assembly by combining said first            product mixture with a stream S3 and allowing said second            product mixture to equilibrate for a HUT-2 seconds; wherein            said stream S3 comprises a metal compound in said process            solvent;        -   c) forming said in-line intermediate branching catalyst            formulation in said first heterogeneous catalyst assembly by            combining said second product mixture with a stream S4 and            allowing said in-line intermediate branching catalyst            formulation to equilibrate for a HUT-3 seconds prior to            injection into said second reactor and optional injection            into said third reactor, wherein said stream S4 comprises an            alkyl aluminum co-catalyst in said process solvent;        -   d) optionally, c) is skipped and said in-line intermediate            branching catalyst formulation is formed inside said second            reactor and optionally inside said third reactor; wherein            said second product mixture is equilibrated for an            additional HUT-3 seconds and injected into said second            reactor and optionally into said third reactor, and said            stream S4 is independently injected into said second reactor            and optionally into said third reactor, and;        -   e) optionally, a second heterogeneous catalyst assembly is            employed wherein a) through c) are conducted to form a            second in-line intermediate branching catalyst formulation            that is injected into said third reactor; optionally said            second in-line intermediate branching catalyst formulation            is formed inside said third reactor according to d);        -   wherein said HUT-1 is from about 5 seconds to about 70            seconds, said HUT-2 is from about 2 seconds to about 50            seconds and said HUT-3 is from about 0.5 to about 15            seconds.

    -   [V]-8. The process as described in [V]-7, wherein;        -   a) said magnesium compound is defined by the formula            Mg(R¹)₂, wherein the R¹ groups may be the same or different;        -   b) said aluminum alkyl is defined by the formula Al(R³)₃,            wherein the R³ groups may be the same or different;        -   c) said chloride compound is defined by the formula R²Cl;        -   d) said metal compound is defined by the formulas M(X)_(n)            or MO(X)_(n), wherein M represents titanium, zirconium,            hafnium, vanadium, niobium, tantalum, chromium, molybdenum,            tungsten, manganese, technetium, rhenium, iron, ruthenium,            osmium or mixtures thereof, O represents oxygen, X            represents a halogen atom and n is an integer that satisfies            the oxidation state of the metal M, and;        -   e) said alkyl aluminum co-catalyst is defined by the formula            Al(R⁴)_(p)(OR⁵)_(q)(X)_(r), wherein the R⁴ groups may be the            same or different, the OR⁵ groups may be the same or            different and (p+q+r)=3, with the proviso that p is greater            than 0;        -   wherein R¹, R², R³, R⁴ and R⁵ represent hydrocarbyl groups            having from 1 to 10 carbon atoms; optionally R² may be a            hydrogen atom.

    -   [V]-9. The process as described in [V]-7, wherein; a molar ratio        of said aluminum alkyl to said magnesium compound in said second        and optionally said third reactor is from about 3.0:1 to about        70:1; a molar ratio of said chloride compound to said magnesium        compound in said second and optionally said third reactor is        from about 1.0:1 to about 4.0:1; a molar ratio of said alkyl        aluminum co-catalyst to said metal compound in said second and        optionally said third reactor is from about 0:1 to about 10:1,        and; a molar ratio of said aluminum alkyl to said metal compound        in said second and optionally said third reactor is from about        0.05:1 to about 2:1.

    -   [V]-10. The process as described in [V]-1, wherein said        intermediate branching catalyst formulation is a batch        intermediate branching catalyst formulation; wherein said batch        intermediate branching catalyst formulation is formed within        said second reactor by injecting a stream S5 and a stream S4        into said second reactor, wherein said stream S4 comprises an        alkyl aluminum co-catalyst in said process solvent and said        stream S5 comprises a batch intermediate branching procatalyst        in said process solvent; optionally said batch intermediate        branching catalyst formulation is employed in said third reactor        by independently injecting said stream S5 and said stream S4        into said third reactor.

    -   [V]-11. The process as described in [V]-10, wherein said alkyl        aluminum co-catalyst is defined by the formula        Al(R⁴)_(p)(OR⁵)_(q)(X)_(r), wherein the R⁴ groups may be the        same or different, the OR⁵ groups may be the same or different        and (p+q+r)=3, with the proviso that p is greater than 0;        wherein R⁴ and R⁵ represent hydrocarbyl groups having from 1 to        10 carbon atoms.

    -   [V]-12. The process as described in [V]-10; wherein said batch        intermediate branching procatalyst comprises:        -   a) a magnesium compound defined by the formula Mg(R¹)₂,            wherein R¹ may be the same or different;        -   b) a chloride compound defined by the formula R²Cl;        -   c) optionally an aluminum alkyl halide defined by the            formula (R⁶)_(v)AlX_(3−v); wherein the R⁶ groups may be the            same or different, X represents a halogen atom, and v is 1            or 2;        -   d) a metal compound defined by the formulas M(X)_(n) or            MO(X)_(n), wherein M represents titanium, zirconium,            hafnium, vanadium, niobium, tantalum, chromium, molybdenum,            tungsten, manganese, technetium, rhenium, iron, ruthenium,            osmium or mixtures thereof, O represents oxygen, X            represents a halogen atom and n is an integer that satisfies            the oxidation state of the metal M;        -   wherein R¹, R² and R⁶ represent hydrocarbyl groups having            from 1 to 10 carbon atoms; optionally R² may be a hydrogen            atom.

    -   [V]-13. The process as described in [V]-12 wherein a molar ratio        of said chloride compound to said magnesium compound in said        batch intermediate branching procatalyst is from about 2:1 to        about 3:1; wherein a molar ratio of said magnesium compound to        said metal compound in said procatalyst is from 5:1 to about        10:1; wherein a molar ratio of said aluminum alkyl halide to        said magnesium compound in said procatalyst is from about 0:1 to        about 0.5:1, and; wherein a molar ratio of said alkyl aluminum        co-catalyst to said metal compound in said procatalyst is from        about 0.5:1 to about 10:1.

Embodiments of this disclosure include articles of manufacture. Not tobe construed as limiting, the ethylene interpolymer products disclosedherein may be converted into manufactured articles comprising a film.Non-limiting examples of processes to manufacture such films includeblown film processes, double bubble processes, triple bubble processes,cast film processes, tenter frame processes and machine directionorientation (MDO) processes. An embodiment of this disclosure,hereinafter embodiment [VI], is fully described immediately below.

-   -   [VI]-1. A film comprising at least one layer comprising an        ethylene interpolymer product comprising at least one ethylene        interpolymer, wherein said ethylene interpolymer is        characterized by an intermediate branching,        -   wherein said intermediate branching is characterized by a            Non-Comonomer Index Distribution, NCID, having a value            characterized by Eq. (1a) and Eq. (1b), wherein, M_(o) is a            peak molecular weight that characterizes a molecular weight            distribution of said ethylene interpolymer when fit to a log            normal distribution; wherein a first derivative of said            NCID_(i),

$\frac{{dNCID}_{i}}{d\log M_{i}},$

-   -   -    Eq. (2), has a value of ≤−0.0001, coefficients β₀, β₃₁, β₂            and β₃ are generated by fitting said NCID_(i) of said            ethylene interpolymer to a third order polynomial, Eq. (3),            and wherein said NCID_(i) may be experimentally measured or            computer simulated.

    -   [VI]-2. The film as described in [VI]-1, wherein said ethylene        interpolymer is synthesized using an intermediate branching        catalyst formulation.

    -   [VI]-3. The film as described in [VI]-2, wherein said        intermediate branching catalyst formulation is an in-line        intermediate branching catalyst formulation or a batch        intermediate catalyst formulation.

    -   [VI]-4. The film as described in [VI]-1, wherein said ethylene        interpolymer product comprises a first ethylene interpolymer, a        second ethylene interpolymer and optionally a third ethylene        interpolymer;        -   wherein at least one of said first, said second and/or said            third ethylene interpolymer is characterized by said            NCID_(i) having a value characterized by Eq. (1a) and Eq.            (1b) and said first derivative Eq. (2) has a value −0.0001,            wherein said NCID_(i) may be experimentally measured or            computer simulated.

    -   [VI]-5. The film as described in [VI]-4, wherein said first        ethylene interpolymer is synthesized with a first heterogeneous        catalyst formulation, said second ethylene interpolymer is        synthesized with a second heterogeneous catalyst formulation and        said optional third ethylene interpolymer is synthesized with a        third heterogeneous catalyst formulation; wherein said first,        said second and said third heterogeneous catalyst formulations        may be the same formulation or different formulations with the        proviso that at least one of said first, said second and/or said        third heterogeneous catalyst formulations is an intermediate        branching catalyst formulation.

    -   [VI]-6. The film as described in [VI]-1, wherein said ethylene        interpolymer is further characterized by a dimensionless Long        Chain Branching Factor, LCBF, having a value <0.001.

    -   [VI]-7. The film as described in [VI]-1, wherein said ethylene        interpolymer product has a melt index from about 0.3 to about 15        dg/minute and a density from about 0.890 to about 0.965 g/cc;        wherein melt index is measured according to ASTM D1238 (2.16 kg        load and 190° C.) and density is measured according to ASTM        D792.

    -   [VI]-8. The film as described in [VI]-1, wherein said ethylene        interpolymer product has a M_(w)/M_(n) from about 2.2 to about        25 and a CDBI₅₀ from about 10% to about 98%.

    -   [VI]-9. The film as described in [VI]-5, wherein:        -   (i) said first ethylene interpolymer has a melt index from            about 0.001 to about 1000 dg/minute, a density from about            0.890 g/cm³ to about 0.965 g/cc and is from about 0 to 60            weight percent of said ethylene interpolymer product;        -   (ii) said second ethylene interpolymer has melt index from            about 0.001 to about 1000 dg/minute, a density from about            0.89 g/cm³ to about 0.965 g/cc and is from about 10 to 99            weight percent of said ethylene interpolymer product; and        -   (iii) optionally said third ethylene interpolymer has a melt            index from about 0.1 to about 10000 dg/minute, a density            from about 0.890 to about 0.965 g/cc and is from 0 to about            30 weight percent of said ethylene interpolymer product;        -   wherein melt index is measured according to ASTM D1238 (2.16            kg load and 190° C.), density is measured according to ASTM            D792 and weight percent is the weight of said first, said            second or said optional third ethylene interpolymer divided            by the weight of said ethylene interpolymer product.

    -   [VI]-10. The film as described in [VI]-1, wherein said ethylene        interpolymer product is manufactured using a solution        polymerization process.

    -   [VI]-11. The film as described in [VI]-1, wherein said ethylene        interpolymer product further comprises from 0.001 to about 10        mole percent of one or more α-olefin; wherein said one or more        α-olefin are C₃ to C₁₀ α-olefins.

    -   [VI]-12. The film as described in [VI]-11, wherein said one or        more α-olefin is 1-hexene, 1-octene or a mixture of 1-hexene and        1-octene.

    -   [VI]-13. The film as described in [VI]-1, wherein said film is a        monolayer film having a dart impact that is from 10% to 110%        higher, relative to a comparative monolayer film; wherein said        comparative monolayer film contains a comparative ethylene        interpolymer that has replaced said ethylene interpolymer;        -   wherein said comparative ethylene interpolymer does not            contain intermediate branching, has a comparative            Non-Comonomer Index Distribution (NCID_(i)®) that does not            satisfy Eq. (1a) and Eq. (1b), and has a comparative first            derivative

$\left( \frac{{dNCID}_{i}}{d\log M_{i}} \right)^{c} > {- {0.0001.}}$

-   -   [VI]-14. The film as described in [VI]-1, wherein said at least        one layer further comprises one or more polyolefin.    -   [VI]-15. The film as described in [VI]-14, wherein said        polyolefin is one or more ethylene polymer, one or more        propylene polymer or a mixture of said ethylene polymer and said        propylene polymer.    -   [VI]-16. The film as described in [VI]-1, wherein said film has        a thickness from 0.5 mil to 10 mil.    -   [VI]-17. The film as described in [VI]-1, wherein said film        comprises from 2 to 11 layers, wherein at least one or more        layer comprises said ethylene interpolymer product having        intermediate branching.

A further embodiment of this disclosure, hereinafter embodiment [VII],is fully described immediately below.

-   -   [VII]-1. A film comprising at least one layer comprising an        ethylene interpolymer product comprising:        -   (i) a first ethylene interpolymer;        -   (ii) a second ethylene interpolymer, and;        -   (iii) optionally a third ethylene interpolymer;        -   wherein said second ethylene interpolymer is characterized            by an intermediate branching, wherein said intermediate            branching is characterized by a Non-Comonomer Index            Distribution, NCID_(i), having a value characterized by Eq.            (1a) and Eq. (1b); wherein, M_(o) is a peak molecular weight            that characterizes a molecular weight distribution of said            second ethylene interpolymer when fit to a log normal            distribution;        -   wherein a first derivative of said NCID_(i),

$\frac{{dNCID}_{i}}{d\log M_{i}},$

-   -   -    Eq. (2), has a value of ≤−0.0001, coefficients β₀, β₁, β₂            and β₃ are generated by fitting said NCID_(i) of said second            ethylene interpolymer to a third order polynomial, Eq. (3),            and wherein said NCID_(i) may be experimentally measured or            computer simulated.

    -   [VII]-2. The film as described in [VII]-1, wherein said first        ethylene interpolymer is synthesized using a homogenous catalyst        formulation and said second ethylene interpolymer is synthesized        using an intermediate branching catalyst formulation.

    -   [VII]-3. The film as described in [VII]-2, wherein said        homogeneous catalyst formulation is an unbridged single site        catalyst formulation or a bridged metallocene catalyst        formulation and said intermediate branching catalyst formulation        is an in-line intermediate branching catalyst formulation or a        batch intermediate branching catalyst formulation.

    -   [VII]-4. The film as described in [VII]-1, wherein said ethylene        interpolymer product has a melt index from about 0.3 to about 15        dg/minute and a density from about 0.858 to about 0.965 g/cc;        wherein melt index is measured according to ASTM D1238 (2.16 kg        load and 190° C.) and density is measured according to ASTM        D792.

    -   [VII]-5. The film as described in [VII]-1, wherein said ethylene        interpolymer product has a M_(w)/M_(n) from about 2 to about 25        and a CDBI₅₀ from about 10% to about 98%.

    -   [VII]-6. The film as described in [VII]-1 wherein;        -   (i) said first ethylene interpolymer has a melt index from            about 0.001 to about 1000 dg/minute, a density from about            0.855 g/cm³ to about 0.975 g/cc and is from about 0 to 60            weight percent of said ethylene interpolymer product;        -   (ii) said second ethylene interpolymer has melt index from            about 0.001 to about 1000 dg/minute, a density from about            0.89 g/cm³ to about 0.965 g/cc and is from about 10 to 99            weight percent of said ethylene interpolymer product        -   (iii) said third ethylene interpolymer has a melt index from            about 0.1 to about 10000 dg/minute, a density from about            0.855 to about 0.975 g/cc and is from 0 to about 30 weight            percent of said ethylene interpolymer product        -   wherein melt index is measured according to ASTM D1238 (2.16            kg load and 190° C.), density is measured according to ASTM            D792 and weight percent is the weight of said first, said            second or said optional third ethylene interpolymer divided            by the weight of said ethylene interpolymer product.

    -   [VII]-7. The film as described in [VII]-1, wherein said ethylene        interpolymer product is manufactured using a solution        polymerization process.

    -   [VII]-8. The film as described in [VII]-1, wherein said ethylene        interpolymer product further comprises from 0.001 to about 10        mole percent of one or more α-olefin; wherein said one or more        α-olefin are C₃ to C₁₀ α-olefins.

    -   [VII]-9. The film as described in [VII]-8, wherein said one or        more α-olefin is 1-hexene, 1-octene or a mixture of 1-hexene and        1-octene.

    -   [VII]-10. The film as described in [VII]-1, wherein said film is        a monolayer film having one or more of the following properties:        -   a) a dart impact from 10% to 110% higher;        -   b) a machine direction tensile strength from 10% to 20%            higher;        -   c) a transverse direction tensile strength from 10% to 20%            higher;        -   d) a 45° gloss from 10% to 110% higher;        -   e) a haze from 10% to 50% lower;        -   relative to a comparative monolayer film, wherein said            comparative monolayer film contains a comparative second            ethylene interpolymer that has replaced said second ethylene            interpolymer;        -   wherein said comparative second ethylene interpolymer does            not contain intermediate branching, has a comparative first            derivative Eq. (2) value >−0.0001.

    -   [VII]-11. The film as described in [VII]-1; wherein said at        least one layer further comprises one or more polyolefin.

    -   [VII]-12. The film as described in [VII]-11, wherein said        polyolefin is one or more ethylene polymer, one or more        propylene polymer or a mixture of said ethylene polymers and        said propylene polymers.

    -   [VII]-13. The film as described in [VII]-1, wherein said film        has a thickness from 0.5 mil to 10 mil.

    -   [VII]-14. The film as described in [VII]-1, wherein said film        comprises from 2 to 11 layers, wherein at least one or more        layer comprises said ethylene interpolymer product having        intermediate branching.

Not to be construed as limiting, the ethylene interpolymer productsdisclosed herein may be converted into rigid manufactured articles suchas containers, bottle caps, hinged closures, toys, recreationalequipment, cable jacketing, tubing, pipe, foamed articles, truck bedliners, pallets and the like. Such rigid manufactured articles maycontain one or more layers comprising the ethylene interpolymer productsdescribed in embodiments fully described above. Such rigid manufacturedarticles may be fabricated using processes that are well-known in theart; non-limiting examples include injection molding, compressionmolding, blow molding, rotomolding, profile extrusion, pipe extrusion,sheet thermoforming and foaming processes employing chemical or physicalblowing agents.

DESCRIPTION OF FIGURES

The following Figures are presented for the purpose of illustratingselected features and embodiments of this disclosure; it beingunderstood that the embodiments represented in these figures are notlimiting.

FIG. 1 compares the NCID_(i) (Non-Comonomer Index Distribution) ofExamples 1 and 4 that have intermediate branching, relative to theNCID_(i) of Comparative 1 that does not contain intermediate branching.

FIG. 2 illustrates the NCID_(i) of Example 1 on the left axis generatedfrom nine TREF fractions (F1 through F9); the right axis shows thenormalized weight fraction of each TREF fraction as well as thecumulative weight fraction.

FIG. 3 illustrates the NCID_(i) of Example 4 on the left axis generatedfrom nine TREF fractions (F1 through F9); the right axis shows thenormalized weight fraction of each TREF fraction as well as thecumulative weight fraction.

FIG. 4 illustrates the NCID_(i) of Comparative 1 on the left axisgenerated from eight TREF fractions (F1 through F8); the right axisshows the normalized weight fraction of each TREF fraction as well asthe cumulative weight fraction.

FIG. 5 plots the NCID_(i) of Example 1, Example 4, Component B ofExample 5 and Component B of Example 10 demonstrating that theseethylene interpolymer products contained intermediate branching; incontrast, Comparative 1 did not contain intermediate branching; Equation(1a) and Equation (1b) are also plotted.

Note: For a comparison purpose, data plotted in FIG. 5 were horizontallyshifted to a same M_(o) value of 60000, i.e. the M_(o) value from thecomponent B of Example 10.

FIG. 6 plots the first derivative of NCID_(i),

$\frac{{dNCID}_{i}}{d\log M_{i}},$

for Example 1, Example 4, Component B of Example 5 and Component B ofExample 10 illustrating

${{\frac{{dNCID}_{i}}{d\log M_{i}}{values}} \leq {- 0.0001}};$

in contrast, the

$\frac{{dNCID}_{i}}{d\log M_{i}}$

of Comparative 1 was >−0.0001. Note: Note: For a comparison purpose,data plotted in FIG. 6 were horizontally shifted to a same M_(o) valueof 60000, i.e. the M_(o) value from the component B of Example 10.

FIG. 7 illustrates the NCID_(i) of Comparative 3 on the left axisgenerated from nine TREF fractions (F1 through F9); the right axis showsthe normalized weight fraction of each TREF fraction as well as thecumulative weight fraction.

FIG. 8 illustrates the NCID_(i) of Comparative 4 on the left axisgenerated from nine TREF fractions (F1 through F9); the right axis showsthe normalized weight fraction of each TREF fraction as well as thecumulative weight fraction.

FIG. 9 illustrates the NCID_(i) of Comparative 5 on the left axisgenerated from six TREF fractions (F1 through F6); the right axis showsthe normalized weight fraction of each TREF fraction as well as thecumulative weight fraction.

FIG. 10 illustrates the NCID_(i) of Example 5 on the left axis generatedfrom eleven TREF fractions (F1 through F11); the right axis shows thenormalized weight fraction of each TREF fraction as well as thecumulative weight fraction.

FIG. 11 compares NCID_(i) values (left axis) of Example 5 (NCID_(i)Exptl, long dashed curve) with a computer simulated NCID_(i) (NCID_(i)Simulation, dotted curve). Simulated Example 5 was a binary blend of: i)44.0 wt % component A having a constant NCID_(i) ^(A) of 0.997, M_(r)was 160000 and (p was 0.850; and ii) 56.0 wt % component B having aNCID_(i) ^(B) where β₀, β₁, β₂, and β3 were 0.97000, −0.00400, 0.00450and −0.00090, respectively, and M_(o) was 65000 and ζ was 0.2620. Themolecular weight distributions (right axis) of component A, component Band the combined (overall) were also plotted.

FIG. 12 illustrates the NCID_(i) of Example 6 on the left axis generatedfrom eleven TREF fractions (F1 through F11); the right axis shows thenormalized weight fraction of each TREF fraction as well as thecumulative weight fraction.

FIG. 13 illustrates the NCID_(i) of Example 7 on the left axis generatedfrom ten TREF fractions (F1 through F10); the right axis shows thenormalized weight fraction of each TREF fraction as well as thecumulative weight fraction.

FIG. 14 illustrates the NCID_(i) of Comparative 6 on the left axisgenerated from nine TREF fractions (F1 through F9); the right axis showsthe normalized weight fraction of each TREF fraction as well as thecumulative weight fraction.

FIG. 15 illustrates the NCID_(i) of Example 10 on the left axisgenerated from nine TREF fractions (F1 through F9); the right axis showsthe normalized weight fraction of each TREF fraction as well as thecumulative weight fraction.

FIG. 16 compares NCID_(i) values (left axis) of Example 10 (NCID_(i)Exptl, long dashed curve) with a computer simulated NCID_(i) (NCID_(i)Simulation, dotted curve). Simulated Example 10 was a binary blend of:i) 50.0 wt % component A having a constant NCID_(i) ^(A) of 0.970, M_(r)of 120000 and φ of 2.600; and ii) 50.0 wt % component B having aNCID_(i) ^(B) where β0, β₁, β₂, and β₃ were 1.0100, −0.0001, 0.0001 and−0.0011, respectively, M_(o) of 60000 and of 0.2400. The molecularweight distributions of component A, component B and the combined(overall) were also plotted (right axis).

FIG. 17 illustrates the NCID_(i) of Example 11 on the left axisgenerated from eight TREF fractions (F1 through F8); the right axisshows the normalized weight fraction of each TREF fraction as well asthe cumulative weight fraction.

FIG. 18 shows the determination of the Long Chain Branching Factor(LCBF). The abscissa plotted was the log of the corrected Zero ShearViscosity (log(ZSV_(c))) and the ordinate plotted was the log of thecorrected Intrinsic Viscosity (log(IV_(c))). Ethylene interpolymerproducts that do not have LCB, or undetectable LCB, fall on the ‘LinearReference Line’. Ethylene polymers having LCB deviate from the referenceline and were characterized by the dimensionless Long Chain BranchingFactor (LCBF). LCBF=(S_(h)×S_(v))/2; where S_(h) and S_(v) arehorizontal and vertical shift factors, respectively.

FIG. 19 illustrates non-limiting embodiments of a continuous solutionpolymerization process employing two continuously stirred reactors(CSTR) wherein an ethylene interpolymer product having intermediatebranching may be produced.

FIG. 20 illustrates non-limiting embodiments of a continuous solutionpolymerization process employing one continuously stirred reactor (CSTR)wherein an ethylene interpolymer product having intermediate branchingmay be produced.

DEFINITION OF TERMS

Other than in the examples or where otherwise indicated, all numbers orexpressions referring to quantities of ingredients, extrusionconditions, etc., used in the specification and claims are to beunderstood as modified in all instances by the term “about.”Accordingly, unless indicated to the contrary, the numerical parametersset forth in the following specification and attached claims areapproximations that can vary depending upon the desired properties thatthe various embodiments desire to obtain. At the very least, and not asan attempt to limit the application of the doctrine of equivalents tothe scope of the claims, each numerical parameter should at least beconstrued in light of the number of reported significant digits and byapplying ordinary rounding techniques. The numerical values set forth inthe specific examples are reported as precisely as possible. Anynumerical values, however, inherently contain certain errors necessarilyresulting from the standard deviation found in their respective testingmeasurements.

It should be understood that any numerical range recited herein isintended to include all sub-ranges subsumed therein. For example, arange of “1 to 10” is intended to include all sub-ranges between andincluding the recited minimum value of 1 and the recited maximum valueof 10; that is, having a minimum value equal to or greater than 1 and amaximum value of equal to or less than 10. Because the disclosednumerical ranges are continuous, they include every value between theminimum and maximum values. Unless expressly indicated otherwise, thevarious numerical ranges specified in this application areapproximations.

All compositional ranges expressed herein are limited in total to and donot exceed 100 percent (volume percent or weight percent) in practice.Where multiple components can be present in a composition, the sum ofthe maximum amounts of each component can exceed 100 percent, with theunderstanding that, and as those skilled in the art readily understand,that the amounts of the components actually used will conform to themaximum of 100 percent.

In order to form a more complete understanding of this disclosure thefollowing terms are defined and should be used with the accompanyingfigures and the description of the various embodiments throughout.

As used herein, the term “monomer” refers to a small molecule that maychemically react and become chemically bonded with itself or othermonomers to form a polymer.

As used herein, the term “α-olefin” is used to describe a monomer havinga linear hydrocarbon chain containing from 3 to 20 carbon atoms having adouble bond at one end of the chain; an equivalent term is “linearα-olefin”.

As used herein, the term “ethylene polymer”, refers to macromoleculesproduced from ethylene and optionally one or more additional monomers;regardless of the specific catalyst or specific process used to make theethylene polymer. In the polyethylene art, the one or more additionalmonomers are called “comonomer(s)” and often include α-olefins. The term“homopolymer” refers to a polymer that contains only one type ofmonomer. Common ethylene polymers include high density polyethylene(HDPE), medium density polyethylene (MDPE), linear low densitypolyethylene (LLDPE), very low density polyethylene (VLDPE), ultralowdensity polyethylene (ULDPE), plastomer and elastomers. The termethylene polymer includes polymers produced in high pressurepolymerization processes; non-limiting examples include low densitypolyethylene (LDPE), ethylene vinyl acetate copolymers (EVA), ethylenealkyl acrylate copolymers, ethylene acrylic acid copolymers and metalsalts of ethylene acrylic acid (commonly referred to as ionomers). Theterm ethylene polymer includes block copolymers which may include 2 to 4comonomers. The term ethylene polymer includes combinations of, orblends of, the ethylene polymers described in this paragraph.

The term “ethylene interpolymer” refers to a subset of polymers withinthe “ethylene polymer” group that excludes polymers produced in highpressure polymerization processes; non-limiting examples of polymersproduced in high pressure processes include LDPE and EVA.

The term “heterogeneous ethylene interpolymer” refers to a subset ofpolymers in the ethylene interpolymer group that are produced usingheterogeneous catalyst formulations; non-limiting examples of whichinclude well-known Ziegler-Natta or chromium catalyst formulations. Thisdisclosure introduces new heterogeneous ethylene interpolymers,characterized as having intermediate branching and synthesized with anintermediate branching catalyst formulation.

The term “homogeneous ethylene interpolymer” refers to a subset ofpolymers in the ethylene interpolymer group that are produced usinghomogeneous catalyst formulations. Typically, homogeneous ethyleneinterpolymers have narrow molecular weight distributions, for exampleSize Exclusion Chromatography (SEC) M_(w)/M_(n) values of less than 2.8;M_(w) and M_(n) refer to weight and number average molecular weights,respectively. In contrast, the M_(w)/M_(n) of heterogeneous ethyleneinterpolymers are typically greater than the M_(w)/M_(n) of homogeneousethylene interpolymers. In general, homogeneous ethylene interpolymersalso have a narrow comonomer distribution, i.e. each macromoleculewithin the molecular weight distribution has similar comonomer content.Frequently, the composition distribution breadth index “CDBI” is used toquantify how the comonomer is distributed within an ethyleneinterpolymer, as well as to differentiate ethylene interpolymersproduced with different catalysts or processes. In this disclosure,“CDBI₅₀” is defined as the percent of ethylene interpolymer whosecomposition is within 50% of the median comonomer composition; thisdefinition is consistent with that described in U.S. Pat. No. 5,206,075assigned to Exxon Chemical Patents Inc. The CDBI₅₀ of an ethyleneinterpolymer can be calculated from TREF curves (Temperature RisingElution Fractionation); the TREF method is described in Wild, et al., J.Polym. Sci., Part B, Polym. Phys., Vol. 20 (3), pages 441-455.Typically, the CDBI₅₀ of homogeneous ethylene interpolymers are greaterthan about 70%. In contrast, the CDBI₅₀ of α-olefin containingheterogeneous ethylene interpolymers are generally lower than the CDBI₅₀of homogeneous ethylene interpolymers. A blend of two or morehomogeneous ethylene interpolymers, that differ in comonomer content,may have a CDBI₅₀ less than 70%; in this disclosure such a blend wasdefined as a homogeneous blend or homogeneous composition. Similarly, ablend of two or more homogeneous ethylene interpolymers, that differ inweight average molecular weight (M_(w)), may have a M_(w)/M_(n) 2.8; inthis disclosure such a blend was defined as a homogeneous blend orhomogeneous composition.

In this disclosure, the term “homogeneous ethylene interpolymer” refersto both linear homogeneous ethylene interpolymers and substantiallylinear homogeneous ethylene interpolymers. In the art, linearhomogeneous ethylene interpolymers are generally assumed to have no longchain branches or an undetectable amount of long chain branches; whilesubstantially linear ethylene interpolymers are generally assumed tohave greater than about 0.01 to about 3.0 long chain branches per 1000carbon atoms. A long chain branch is macromolecular in nature, i.e.similar in length to the macromolecule that the long chain branch isattached to. In this disclosure the amount of long chain branchingpresent in an ethylene interpolymer was characterized by the ‘Long ChainBranching Factor (LCBF)’. The measurement of LCBF was fully described inthis disclosure.

In this disclosure a new class of ethylene interpolymers are disclosed;specifically, ethylene interpolymers having “intermediate branching”.Intermediate branching was defined as branching that was longer than thebranch length resulting from comonomer incorporation (e.g. C₄ or C₆branches resulting from the incorporation of 1-hexene or 1-octenecomonomers into a propagating macromolecule, respectively) and shorterthan the entanglement molecular weight, M_(e). M_(e) is a well-knownconcept in polymer physics (for example reported to be about 1 kg/molfor polyethylenes, see Fetters et al., Macromolecules 1999, 32, 6847).The amount of intermediate branching in ethylene interpolymers wascharacterized by the ‘Non-Comonomer Index (NCI)’, as well as the‘Non-Comonomer Index Distribution (NCID_(i)), which was determined bytriple detection cross fractionation chromatography (3D-CFC) analysis,as fully described in this specification.

In this disclosure the term ‘ethylene interpolymer product’ refers tothe final product produced by a polymerization process; wherein theethylene interpolymer product has intermediate branching, ascharacterized by the Non-Comonomer Index Distribution (NCID_(i)). Thepolymerization processes disclosed hereinafter include processesemploying one or more polymerization reactor(s). In the case of onereactor employing one intermediate branching catalyst formulation, thefinal product is an ethylene interpolymer product containing oneethylene interpolymer containing intermediate branching. In the case oftwo reactors employing the same intermediate branching catalystformulation, the final product is an ethylene interpolymer productcontaining two ethylene interpolymers both containing intermediatebranching. In the case of two reactors, employing two catalystformulations where one is an intermediate branching catalystformulation, the final product is an ethylene interpolymer productcontaining two ethylene interpolymers; wherein one ethylene interpolymercontains intermediate branching. In the case of a polymerizationprocesses employing three reactors, the ethylene interpolymer productcontained a first, second and third ethylene interpolymer; wherein atleast one of the first, second or third ethylene interpolymer containedintermediate branching. Intermediate branching was produced by anintermediate branching catalyst formulation(s) disclosed hereinafter.

In this disclosure the term ‘component’ was also used; the termcomponent applies to an ethylene interpolymer where the molecular weightdistribution was defined by a mathematical function; i.e. a ‘componentA’ synthesized employing one catalyst formulation and one reactor. Inthis disclosure, the term component also referred to chemical compoundsrequired to manufacture a catalyst formulation; e.g. ‘component (i)’.

In this disclosure the term ‘homogeneous catalyst’ refers to thechemical compound containing the catalytic metal which is frequentlycalled a ‘metal-ligand complex’. In this disclosure, a homogeneouscatalyst is defined by the characteristics of the resulting ethyleneinterpolymer. More specifically, a catalyst was a homogeneous catalystif it produced a homogeneous ethylene interpolymer that has a narrowmolecular weight distribution (SEC M_(w)/M_(n) values of less than 2.8)and a narrow comonomer distribution (CDBI₅₀>70%). Homogeneous catalystsare well known in the art. Two subsets of the homogeneous catalystsinclude unbridged metallocene catalysts and bridged metallocenecatalysts. Unbridged metallocene catalysts are characterized by twobulky ligands bonded to the catalytic metal, a non-limiting exampleincludes bis(isopropyl-cyclopentadienyl) titanium dichloride. In thisdisclosure, an ‘unbridged metallocene catalyst formulation’ comprised anunbridged metallocene catalyst. In bridged metallocene catalysts the twobulky ligands are covalently bonded (bridged) together, a non-limitingexample includes diphenylmethylene (cyclopentadienyl)(2,7-di-t-butylfuorenyl) titanium dichloride; where thediphenylmethylene group bonds, or bridges, the cyclopentadienyl andfluorenyl ligands together. In this disclosure, a ‘bridged metallocenecatalyst formulation’ comprised an bridged metallocene catalyst. Twoadditional subsets of homogeneous catalysts include unbridged andbridged single site catalysts. In this disclosure, single site catalystsare characterized as having only one bulky ligand bonded to thecatalytic metal. A non-limiting example of an unbridged single sitecatalyst includes cyclopentadienyl tri(tertiary butyl)phosphiniminetitanium dichloride; wherein cyclopentadienyl was the bulky ligand. Inthis disclosure, an ‘unbridged single site catalyst formulation’comprised an unbridged single site catalyst. A non-limiting example of abridged single site catalyst includes [C₅(CH₃)₄—Si(CH₃)₂—N(tBu)]titanium dichloride, where the —Si(CH₃)₂— group functions as thebridging group. In this disclosure, a ‘bridged single site catalystformulation’ comprised a bridged single site catalyst.

Herein, the term “polyolefin” includes ethylene polymers and propylenepolymers; non-limiting examples of “propylene polymers” includeisotactic, syndiotactic and atactic propylene homopolymers, randompropylene copolymers containing at least one comonomer (e.g. α-olefins)and impact polypropylene copolymers or heterophasic polypropylenecopolymers.

The term “thermoplastic” refers to a polymer that becomes liquid whenheated, will flow under pressure and solidify when cooled. Thermoplasticpolymers include ethylene polymers as well as other polymers used in theplastic industry; non-limiting examples of other polymers commonly usedin film applications include barrier resins (EVOH), tie resins,polyethylene terephthalate (PET), polyamides and the like.

As used herein the term “monolayer film” refers to a film containing asingle layer of one or more thermoplastics. The term “multilayer film”refers to a film containing more than one layer; non-limiting processesto produce such films include coextrusion or lamination.

As used herein, the terms “hydrocarbyl”, “hydrocarbyl radical” or“hydrocarbyl group” refers to linear, branched, or cyclic, aliphatic,olefinic, acetylenic and aryl (aromatic) radicals comprising hydrogenand carbon that are deficient by one hydrogen.

As used herein, an “alkyl radical” includes linear, branched and cyclicparaffin radicals that are deficient by one hydrogen radical;non-limiting examples include methyl (—CH₃) and ethyl (—CH₂CH₃)radicals. The term “alkenyl radical” refers to linear, branched andcyclic hydrocarbons containing at least one carbon-carbon double bondthat is deficient by one hydrogen radical.

As used herein, the term “aryl” group includes phenyl, naphthyl, pyridyland other radicals whose molecules have an aromatic ring structure;non-limiting examples include naphthylene, phenanthrene and anthracene.An “arylalkyl” group is an alkyl group having an aryl group pendantthere from; non-limiting examples include benzyl, phenethyl andtolylmethyl; an “alkylaryl” is an aryl group having one or more alkylgroups pendant there from; non-limiting examples include tolyl, xylyl,mesityl and cumyl.

As used herein, the phrase “heteroatom” includes any atom other thancarbon and hydrogen that can be bound to carbon. A“heteroatom-containing group” is a hydrocarbon radical that contains aheteroatom and may contain one or more of the same or differentheteroatoms. In one embodiment, a heteroatom-containing group is ahydrocarbyl group containing from 1 to 3 atoms selected from the groupconsisting of boron, aluminum, silicon, germanium, nitrogen,phosphorous, oxygen and sulfur. Non-limiting examples ofheteroatom-containing groups include radicals of imines, amines, oxides,phosphines, ethers, ketones, oxoazolines heterocyclics, oxazolines,thioethers, and the like. The term “heterocyclic” refers to ring systemshaving a carbon backbone that comprise from 1 to 3 atoms selected fromthe group consisting of boron, aluminum, silicon, germanium, nitrogen,phosphorous, oxygen and sulfur.

As used herein the term “unsubstituted” means that hydrogen radicals arebounded to the molecular group that follows the term unsubstituted. Theterm “substituted” means that the group following this term possessesone or more moieties that have replaced one or more hydrogen radicals inany position within the group; non-limiting examples of moieties includehalogen radicals (F, Cl, Br), hydroxyl groups, carbonyl groups, carboxylgroups, amine groups, phosphine groups, alkoxy groups, phenyl groups,naphthyl groups, C₁ to C₁₀ alkyl groups, C₂ to C₁₀ alkenyl groups, andcombinations thereof. Non-limiting examples of substituted alkyls andaryls include: acyl radicals, alkylamino radicals, alkoxy radicals,aryloxy radicals, alkylthio radicals, dialkylamino radicals,alkoxycarbonyl radicals, aryloxycarbonyl radicals, carbomoyl radicals,alkyl- and dialkyl-carbamoyl radicals, acyloxy radicals, acylaminoradicals, arylamino radicals and combinations thereof.

Herein the term “R1” and its superscript form “^(R1)” refers to a firstpolymerization reactor in a continuous solution polymerization process;it being understood that R1 is distinctly different from the symbol R¹;the latter is used in chemical formula, e.g. representing a hydrocarbylgroup. Similarly, the term “R2” and it's superscript form “^(R2)” refersto a second reactor, and; the term “R3” and it's superscript form“^(R3)” refers to a third reactor.

DETAILED DESCRIPTION

Non-Comonomer Index (NCI) and Non-Comonomer Index Distribution(NCID_(i))

FIG. 1 compared the Non-Comonomer Index Distribution (NCID_(i)) ofExamples 1 and 4 with Comparative 1. Examples 1 and 4 as well asComparative 1 did not contain long chain branching (LCB) (or containedan undetectable level of LCB) as evidenced by the Long Chain BranchingFactor (LCBF) discussed below. Examples 1 and 4 contained intermediatebranching as evidenced by NCID_(i) values less than or equal to 0.99. Incontrast, Comparative 1 did not contain intermediate branching asevidenced by NCID_(i) values greater than 0.99. Examples 1 and 4 wereethylene/1-octene interpolymer products (about 0.92 g/cm³ and about 1.0I₂ (melt index, ASTM 1239, 2.16 kg load, 190° C.) produced in acontinuous solution polymerization process using different embodimentsof intermediate branching catalyst formulations. The solution processconditions required to manufacture Examples 1 and 4 are discussed belowand disclosed in Tables 1a and 1b. Comparative 1 was anethylene/1-octene interpolymer (about 0.92 g/cm³ and about 1.0 I₂)produced in a competitive solution polymerization process using acomparative batch Ziegler-Natta catalyst formulation; Comparative 1 wasDowlex 2045G available from The Dow Chemical Company (Midland, Mich.,USA). The physical properties of Examples 1, 2 and 4 and Comparatives 1and 2 were summarized in Table 2. In this disclosure Comparative 2 wasalso Dowlex 2045; however, a different lot (or batch) relative toComparative 1.

In this disclosure, Triple Detection Cross Fractionation Chromatography(3D-CFC) was used to measure NCI and NCID. NCI and NCID_(i) weredimensionless parameters. The testing methods section of this disclosurefully described the 3D-CFC technique. NCI was defined as the measuredMark-Houwink constant (K_(m)) of the sample under test (measured in1,2,4-trichlorobenzene (TCB) at 140° C.) divided by the short chainbranching (SCB) corrected Mark-Houwink constant (K_(co)) for linearethylene/α-olefin interpolymers, as defined by Eq. (6).

$\begin{matrix}{{NCI} = {\frac{K_{m}}{K_{co}} = \frac{1000000\left( {\lbrack\eta\rbrack/M_{v}^{0.725}} \right)}{\left( {391.98 - {A \times {SCB}}} \right)}}} & {{Eq}.(6)}\end{matrix}$

In Eq. (6), [η] was the experimentally measured intrinsic viscosity(dL/g) as determined by 3D-SEC, My was the viscosity average molar mass(g/mol) as determined by 3D-SEC; SCB was the short chain branchingcontent (number of CH₃ groups per 1000 carbon atoms [CH₃#/1000C]) asdetermined by FTIR; and A was a constant that depended on the α-olefinpresent in the ethylene/α-olefin interpolymer under test; A was 2.1626for 1-octene. In the case of an ethylene homopolymer no correction wasrequired for the Mark-Houwink constant, i.e. SCB is zero.

Using a Polymer Char Crystaf-TREF unit an ethylene/α-olefin interpolymersample under test was fractionated into a number of fractions (typicallyfrom 5 to 20 fractions, in this disclosure superscript f, i.e. ^(f),represents the fraction number) and the Non-Comonomer Index Distribution(NCID_(i)) was determined. Specifically: (i) the NCI of each fraction(NCI^(f)) was calculated using Eq. (4) (Equation (4) was introducedpreviously and was reproduced below);

$\begin{matrix}{{NCI}^{f} = {\frac{K_{m}^{f}}{K_{co}} = \frac{1000000\left( {\lbrack\eta\rbrack^{f}/\left( M_{v}^{f} \right)^{0.725}} \right)}{\left( {391.98 - {{Ax}\left( {{BxT}^{f} + C} \right)}} \right.}}} & {{Eq}.(4)}\end{matrix}$

where A, B and C were constants determined experimentally and T^(f) wasthe weight average TREF elution temperature of fraction f (see testingmethods section for additional detail), and; (ii) the Non-ComonomerIndex Distribution (NCID_(i)) was calculated using Eq. (5) (introducedpreviously);

NCID_(i)=Σ₁ ^(f)(wt.fr.)^(f)(w _(i) log(M _(i)))^(f)×NCI^(f)  Eq.(5)

where (wt.fr.)^(f) represented the weight fraction of f^(th) TREFfraction, and; (w_(i) log(M_(i)))^(f) represented the weight fraction ofthe f^(th) TREF fraction having molar mass M_(i). Clarifying with anexample, 3D-CFC results for Example 1 were disclosed in Table 3. Asshown in Table 3, Example 1 was fractionated into nine fractions (F1through F9), the NCI^(f) of each fraction was calculated using Eq. (4).TREF fraction 1 (F1) was eluted from 30° C. to 60° C. and was 0.1699weight fraction {(wt.fr)¹} of Example 1. Again, (w_(i) log(M_(i)))¹ wasthe weight fraction of F1 having molar mass M_(i); further, (w_(i)log(M_(i)))¹ summed over all i characterized the molecular weightdistribution of F1. Typically, the molecular weight distribution of eachfraction contained about 300 data points, employing log(M_(i))increments of 0.01. As shown in Table 3, fraction F1 (of Example 1) hada weight average molecular weight (M_(w)) of 72,300 g/mol, a viscosityaverage molecular weight (M_(v)) of 63,700 g/mol, an intrinsic viscosity[η] of 0.98 dL/g, the amount of short chain branching (SCB^(f)) was29.03 CH₃/1000C and the Non-Comonomer Index of Fraction 1 (NCI¹) was0.983. The 3D-CFC TREF fractions isolated from Example 1 hadNon-Comonomer Index values (NCI^(f)) that varied from 0.983 to 0.902.

Graphically, FIG. 2 shows the Non-Comonomer Index Distribution(NCID_(i)) of Example 1 (left y-axis), and; the molecular weightdistributions of the nine 3D-CFC TREF fractions and cumulative (overall)molecular weight distribution (right y-axis). Example 1 was anethylene/1-octene interpolymer containing intermediate branching asevidenced by NCID_(i) values 0.99. As shown in Tables 1a and 1b, Example1 was produced by injecting an in-line intermediate branching catalystformulation into reactor 2 (R2); 80% of the ethylene and 100% of the1-octene was injected into R2; 20% of the ethylene was injected intoreactor 3 (R3); a catalyst formulation was not injected into R3.

As shown in Tables 1a and 1b, Example 4 was produced using a batchintermediate branching catalyst formulation; Table 2 summarized thephysical characteristics of Example 4. The 3D-CFC analysis of Example 4was summarized in Table 4. Nine 3D-CFC TREF fractions were collected;fraction 1 (F1) was collected at TREF elution temperatures from 30° C.to 60° C. and was 0.1666 weight fraction (wt.fr.)¹ of Example 4. F1 hada weight average molecular weight (M_(w)) of 61,600 g/mol, a viscosityaverage molecular weight (M_(v)) of 54,400 g/mol, an intrinsic viscosity[1] of 0.88 dL/g, the amount of short chain branching (SCB^(f)) was29.42 CH₃/1000C and the Non-Comonomer Index of Fraction 1 (NCI¹) was0.985. The 3D-CFC TREF fractions isolated from Example 4 hadNon-Comonomer Index values (NCI^(f)) that varied from 0.985 to 0.938.FIG. 3 showed the NCID_(i) of Example 4 as a function of Log(MolarMass), as well as the molecular weight distributions of the nine 3D-CFCTREF fractions and the cumulative (overall) molecular weightdistribution. Example 4 contained intermediate branching as evidenced byNCID_(i) values ≤0.99.

Table 5 summarized 3D-CFC analysis of Comparative 1 and physicalcharacteristics were summarized in Table 2. Comparative 1 wasfractionated into eight 3D-CFC TREF fractions; fraction 1 (F1) collectedfrom 30° C. to 65° C. was 0.1921 weight fraction ((wt.fr.)¹) ofComparative 1. F1 had a weight average molecular weight (M_(w)) of60,400 g/mol, a viscosity average molecular weight (M_(v)) of 51,700g/mol, an intrinsic viscosity [η] of 0.87 dL/g, the amount of shortchain branching (SCB^(f)) was 26.63 CH₃/1000C and the Non-ComonomerIndex value of Fraction 1 (NCI¹) was 1.00. Comparative 1 fractions hadan average NCI of 0.998±0.005. FIG. 4 plotted the Non-Comonomer IndexDistribution (NCID_(i)) of Comparative 1 as a function of Log(MolarMass), the molecular weight distributions of the eight 3D-CFC TREFfractions and the cumulative molecular weight distribution; NCID₁ valueswere consistently greater than 0.99. Comparative 1 did not containintermediate branching as evidenced by NCID_(i) values >0.99.

Using various embodiments of intermediate branching catalystformulations, ethylene interpolymer products having a range ofintermediate branching were produced. This range in intermediatebranching was characterized by the Non-Comonomer Index Distribution(NCID_(i)) as shown in FIG. 5 (again, Comparative 1 in FIG. 5 (longdash-dot line) did not contain intermediate branching, i.e. NCIDvalues >0.99). The experimentally measured NCID_(i) of Example 1 was fitto the following third order polynomial, Eq. (3) (introducedpreviously);

NCID_(i)=β₀+β₁(log M _(i)−log M _(o)+4.93)+β₂(log M _(i)−log M_(o)+4.93)²+β₃(log M _(i)−log M _(o)+4.93)³  Eq.(3)

and this fit produced the Example 1 curve (dotted curve) plotted in FIG.5 ; where β₀, β₁, β₂ and β₃ were 0.98658, −0.00388, 0.00313 and−0.00069, respectively, and M_(o) was 85000. M_(o) was the peakmolecular weight that characterized the molecular weight distribution ofExample 1 when fit to the log normal distribution (described below).Similarly, the experimentally measured NCID_(i) of Example 4 was fit toEq. (3) producing the short dash-dot curve plotted in FIG. 5 ; where β₀,β₁, β₂ and β₃ were 0.98945, −0.00201, 0.00137 and −0.00034,respectively, and M_(o) was 82000. FIG. 5 also plotted the computersimulated NCID_(i) of component B of Example 5 (short dashed curved);where β₀, β₁, β₂ and β₃ were 0.97000, −0.00400 0.00450 and −0.00090,respectively, and M_(o) was 65000. Example 5 was fully described below,in brief, Example 5 (manufactured in a dual reactor solution process)contained a first and a second ethylene interpolymer, i.e. components Aand B, respectively. Example 5's component B contained intermediatebranching and component A did not contain intermediate branching. Theterm ‘computer simulated’ means the NCID_(i) of component B (in Example5) was generated by deconvolution (fully described below). FIG. 5 alsoplotted the computer simulated NCDI_(i) of component B in Example 10(long dash−dot−dot curve); where so, β₁, β₂ and β₃ were 1.0100, −0.0001,0.0001 and −0.0011, respectively, and M_(o) was 60000.

Given these examples, intermediately branched ethylene interpolymerproducts had NCID_(i) values characterized by Eq. (1a) and Eq. (1b)(both introduced previously):

NCID_(i)≤1.000−0.00201(log M _(i)−log M _(o)+4.93)+0.00137(log M_(i)−log M _(o)+4.93)²−0.00034(log M _(i)−log M _(o)+4.93)³  Eq.(1a)

NCID_(i)≥0.730−0.00388(log M _(i)−log M _(o)+4.93)+0.00313(log M_(i)−log M _(o)+4.93)²−0.00069(log M _(i)−log M _(o)+4.93)³  Eq.(1b)

Eq. (1a) was plotted in FIG. 5 (solid curve), as was Eq. (1b) (long dashcurve); where M_(o) was 60000. In alternative words, ethyleneinterpolymer products having intermediate branching had NCID_(i) valuescharacterized as follows: Eq. (1b)≤NCID_(i)≤Eq. (1a).

An additional feature that characterized intermediately branchedethylene interpolymer products was the first derivative of Eq. (3), i.e.Eq. (2) (introduced previously):

$\begin{matrix}{\frac{{dNCID}_{i}}{d\log M_{i}} = {\beta_{1} + {2{\beta_{2}\left( {{\log M_{i}} - {\log M_{0}} + 4.93} \right)}} + {3{\beta_{3}\left( {{\log M_{i}} - {\log M_{0}} + 4.93} \right)}^{2}}}} & {{Eq}.(2)}\end{matrix}$

FIG. 6 compares the

$\frac{{dNCID}_{i}}{d\log M_{i}}$

values of Example 1 (dotted curve), Example 4 (dash-dot curve),component B of Example 5 (dash curve), component B of Example 10 (solidcurve) with comparative 1 (dash-dot-dot line). Evidently,

$\frac{{dNCID}_{i}}{d\log M_{i}}$

was negative for intermediately branched ethylene interpolymer products.In contrast,

$\frac{{dNCID}_{i}}{d\log M_{i}}$

of Comparative 1 was zero; more specifically, statistically the NCID_(i)values of Comparative 1 shown in FIG. 5 were best represented by a oneparameter intercept model (i.e. a constant, the mean 0.998), thus

$\frac{{dNCID}_{i}}{d\log M_{i}}$

of Comparative 1 was zero. As shown in FIG. 6 ,

$\frac{{dNCID}_{i}}{d\log M_{i}}$

of the disclosed ethylene interpolymer products was consistently≤−0.0001; in contrast, Comparative 1 had

${\frac{{dNCID}_{i}}{d\log M_{i}}{values}} > {- {0.0001.}}$

Table 6 summarized the 3D-CFC analysis of Comparative 3 and additionalphysical and molecular characteristics were shown in Table 7.Comparative 3 was a dual reactor ethylene/1-octene interpolymermanufactured in a dual reactor solution polymerization process using anunbridged single site catalyst formulation comprising cyclopentadienyltri(tertiary butyl)phosphinimine titanium dichloride, i.e. SURPASS®FPs117-C available from NOVA Chemicals Company (Calgary, Alberta,Canada). In Comparative 3 the comonomer was randomly distributed andComparative 3 did not contain long chain branching (LCB) (or containedan undetectable level of LCB) as evidenced by the Long Chain BranchingFactor (LCBF) (discussed below). Comparative 3 was fractionated intonine 3D-CFC TREF fractions; fraction 1 (F1) was collected from 30° C. to65° C. and was 0.1527 weight fraction (wt.fr.)¹. Fraction F1 had aweight average molecular weight (M_(w)) of 23,800 g/mol, a viscosityaverage molecular weight (M_(v)) of 22,200 g/mol, an intrinsic viscosity[η] of 0.48 dL/g, the amount of short chain branching (SCB^(f)) was24.98 CH₃/1000C and the Non-Comonomer Index value of Fraction 1 (NCI¹)was 0.998. The 3D-CFC TREF fractions isolated from Comparative 3 hadNCI^(f) values that varied from 1.00 to 0.994. FIG. 7 plottedComparative 3's NCID_(i) values as a function of Log(Molar Mass). TheNCID_(i) of Comparative 3 was characterized by a constant (i.e. the mean0.997); thus

$\frac{{dNCID}_{i}}{{dM}_{i}}$

of Comparative 3 was zero. Comparative 3 did not contain intermediatebranching as evidenced by NCID_(i) values >0.99.

Table 8 summarizes 3D-CFC analysis of Comparative 4 and physicalcharacteristics were summarized in Table 7. Comparative 4 was acompetitive ethylene/1-octene interpolymer produced using a single-sitecatalyst formation in a single reactor solution process, i.e. AFFINITYPL1880 available from The Dow Chemical Company (Midland, Mich., USA). Inaddition to short chain branching (i.e. C₆ branching from the 1-octenecomonomer), Comparative 4 also contained long chain branching (LCB); asevidenced by the Long Chain Branching Factor (LCBF) (discussed below).The Non-Comonomer Index (NCI), as defined by Eq. (6), was influenced bythe amount of long chain branching; with NCI decreasing as LCBincreased. As shown in Table 8, Comparative 4 was fractionated into nine3D-CFC TREF fractions; fraction 1 (F1) collected from 30° C. to 50° C.was 0.1123 weight fraction (wt.fr.)¹. Fraction F1 had a weight averagemolecular weight (M_(w)) of 45,900 g/mol, a viscosity average molecularweight (M_(v)) of 43,900 g/mol, an intrinsic viscosity [η] of 0.70 dL/g,the amount of short chain branching (SCB^(f)) was 33.91 CH₃/1000C andthe Non-Comonomer Index value of Fraction 1 (NCI¹) was 0.944. The 3D-CFCTREF fractions isolated from Comparative 4 had consistent NCI^(f)values, i.e. 0.945±0.003. FIG. 8 plotted Comparative 4's NCID_(i) valuesas a function of Log(Molar Mass); statistically these NCID_(i) valueswere best represented by a one parameter (the mean, 0.945) interceptmodel thus

$\frac{{dNCID}_{i}}{d\log M_{i}}$

was zero.

Table 9 summarizes 3D-CFC analysis of Comparative 5 and physicalcharacteristics were summarized in Table 7. Comparative 5 was anethylene/1-octene interpolymer produced in the solution pilot plantdisclosed herein using one reactor and a bridged metallocene catalystformulation comprising diphenylmethylene (cyclopentadienyl)(2,7-di-t-butylfuorenyl) hafnium dimethyl. Comparative 5 contained longchain branching (LCB); as evidenced by LCBF data (discussed below).Comparative 5 was fractionated into six 3D-CFC TREF fractions; fraction1 (F1) collected from 30° C. to 55° C. was 0.1153 weight fraction(wt.fr.)¹. Fraction F1 had a weight average molecular weight (M_(w)) of37,700 g/mol, a viscosity average molecular weight (M_(v)) of 35,900g/mol, an intrinsic viscosity [η] of 0.64 dL/g, the amount of shortchain branching (SCB^(f)) was 30.95 CH₃/1000C and the Non-ComonomerIndex value of Fraction 1 (NCI¹) was 0.976. The 3D-CFC TREF fractionsisolated from Comparative 5 had consistent NCI^(f) values, i.e.0.975±0.002. The flat (constant) Non-Comonomer Index Distribution(NCID_(i)) of Comparative 5 was plotted in FIG. 9 ; statistically theseNCID_(i) values were best represented by a one parameter (the mean,0.975) intercept model thus Comparative 5's

$\frac{{dNCID}_{i}}{d\log M_{i}}$

was zero.

In some cases the polymer sample under test contained one component. Theterm ‘component’ referred to an ethylene interpolymer having adistribution of molecular weights produced by one catalyst systeminjected into one reactor. In other cases, the polymer sample containedmore than one component; for example, a polymer sample produced byinjecting more than one catalyst formulation into one reactor, or apolymer sample produced using more than one reactor (where the same ordifferent catalyst(s) are used in the multiple reactors).

Tables 10a and 10b summarized the solution process conditions used tomanufacture Example 5 and Table 11 disclosed the physicalcharacteristics. Example 5 was a dual reactor and dual catalystethylene/1-octene interpolymer product containing: about 44% of acomponent A produced in a first reactor (R1) using an unbridged singlesite catalyst formulation, and; about 56% of a component B produced in asecond reactor (R2) using an embodiment of an in-line intermediatebranching catalyst formulation. In Example 5, the two reactors (R1 andR2) were operated in series mode. Table 12 summarized 3D-CFC analysis ofExample 5. Example 5 was fractionated into eleven 3D-CFC TREF fractions;fraction 5 (F5) collected from 71° C. to 73° C. was 0.0992 weightfraction (wt.fr.)⁵. Fraction F5 had a weight average molecular weight(M_(w)) of 140,600 g/mol, a viscosity average molecular weight (M_(v))of 132,100 g/mol, an intrinsic viscosity [η] of 1.84 dL/g, the amount ofshort chain branching (SCB^(f)) was 15.10 CH₃/1000C and theNon-Comonomer Index value of Fraction 5 (NCI⁵) was 0.992. The NCID_(i)of Example 5 was plotted in FIG. 10 (left vertical axis), as well as themolecular weight distributions of eleven 3D-CFC TREF fractions andcumulative (overall) molecular weight distribution (right verticalaxis). Component B in Example 5 contained intermediate branchingproduced by an embodiment of an in-line intermediate branching catalystformulation. The shape of the NCID_(i) in FIG. 10 reflected thefollowing facts: (1) component B's intermediate branching tended toreduce NCI values monotopically as Log(Molar Mass) increased as shown inFIG. 5 and

$\frac{{dNCID}_{i}}{d\log M_{i}}$

of component B was ≤−0.0001 as shown in FIG. 6 , and; (2) the NCID_(i)of component A was a constant 0.997 and

$\frac{{dNCID}_{i}}{d\log M_{i}}$

of component A was zero (>−0.0001).

In FIG. 10 the peak in Example 5's NCID_(i) at about 5.5 Log(Molar Mass)reflected the fact that component A was higher molecular weight thancomponent B; as supported by FIG. 11 . FIG. 11 illustrated a computersimulation of Example 5 showing the NCID_(i) distribution of a binaryblend of: i) 44.0 wt % component A having a constant NCID_(i) ^(A) of0.997, and, ii) 56.0 wt % component B having a NCID_(i) ^(B) defined byEq. (3), where β₀, β₁, β₂, and β₃ were 0.97000, −0.00400, 0.00450 and−0.00090, respectively, and M_(o) was 65000; component B was alsocharacterized by

${\frac{{dNCID}_{i}}{d\log M_{i}}{values}} \leq {- {0.0001.}}$

The computer simulation was a good representation of Example asevidenced by the similarity between the experimentally measured NCID_(i)values (long dash curve) and the simulated NCID_(i) values (dottedcurve) in FIG. 11 .

The simulated NCID_(i) values shown in FIG. 11 were generated using Eq.(7)

$\begin{matrix}{{NCID}_{i} = {{\sum\limits_{i}{\left( {{wt}.{fr}.} \right)^{A}\left( {w_{i}M_{i}} \right)^{A}{NCID}_{i}^{A}}} + {\left( {{wt}.{fr}.} \right)^{B}\left( {w_{i}M_{i}} \right)^{B}{NCID}_{i}^{B}}}} & {{Eq}.(7)}\end{matrix}$

where (wt.fr.)^(A) and (wt.fr.)^(B) represented the weight fractions ofcomponents A and B, respectively, with the proviso that((wt.fr.)^(A)+(wt.fr.)^(B)=1.0); (w_(i)M_(i))^(A) was the weightfraction of component A having molecular weight M_(i) defined by amodified Flory-Schultz distribution Eq. (8); NCID_(i) ^(A) was theNon-Comonomer Index Distribution of component A (in the case of Example5's component A, NCID_(i) was a constant 0.997); (w_(i)M_(i))^(B) wasthe weight fraction of component B having molecular weight M_(i) definedby a log normal distribution Eq. (9) and; NCID_(i) ^(B) was theNon-Comonomer Index Distribution of component B as defined above.

The modified Flory-Shultz distribution was defined as follows:

$\begin{matrix}{\left( {w_{i}M_{i}} \right)^{A} = {{\ln(10)} \times \left( \frac{M_{i}}{M_{r}} \right){\exp\left( {\varphi - \frac{M_{i}}{M_{r}}} \right)}}} & {{Eq}.(8)}\end{matrix}$

where M_(r) and φ were fitting parameters, i.e. M_(r) was a referencemolecular weight and φ a breadth parameter. In the case of Example 5'scomponent A, M_(r) was 160000 and φ was 0.850.

The log-normal distribution was defined as follows:

$\begin{matrix}{\left( {w_{i}M_{i}} \right)^{B} = {\frac{1}{{\xi\left( {2\pi} \right)}^{\frac{1}{2}}}{\exp\left( {{- \left( \frac{1}{2} \right)}\left( {\left( {{\log M_{i}} - {\log M_{o}}} \right)/\xi} \right)^{2}} \right)}}} & {{Eq}.(9)}\end{matrix}$

where M_(o) and ζ were fitting parameters, i.e. M_(o) was the peakmolecular weight and ζ was a breadth parameter. In the case of Example5's component B, M_(o) was 65000 and ζ was 0.2620.

In this disclosure the NCID_(i) of an ethylene interpolymer product maybe ‘experimentally measured’ or ‘computer simulated’. FIG. 2 and Table 3demonstrated how to determine the ‘experimentally measured’ NCID_(i) forExample 1; in this case, NCID_(i) could be measured directly (i.e.experimentally measured) because Example 1 contained only one ethyleneinterpolymer. However, in the case of an ethylene interpolymer productcontaining more than one ethylene interpolymer, the NCID_(i) wasdetermined by computer simulation, or deconvolution, as demonstrated byExample 5 in FIG. 11 ; i.e. a computer was used to fit Eq. (7) to theexperimentally measured NCID_(i) of Example 5 to determine the β₀, β₁,β₂ and β₃ values of Example 5's component B for use in Eq. (2) and Eq.(3).

The 3D-CFC analysis of Example 6 was summarized in Table 13 and FIG. 12; the physical characteristics of Example 6 were summarized in Table 11.Example 6 was a dual reactor ethylene/1-octene interpolymer produced ina commercial solution polymerization plant. Example 6 contained about 40wt % of a component A and about 60 wt % of a component B; component Awas produced in a first reactor (R1) using an unbridged single sitecatalyst formulation and component B was produced in a second reactor(R2) using an embodiment of an in-line intermediate branching catalystformulation; R1 and R2 were operated in series mode. As shown in Table13, Example 6 was fractionated into eleven 3D-CFC TREF fractions;fraction 1 (F1) collected at TREF elution temperatures from 30° C. to51° C. was 0.0993 weight fraction (wt.fr.)¹. Fraction F1 had a weightaverage molecular weight (M_(w)) of 61,800 g/mol, a viscosity averagemolecular weight (M_(v)) of 56,400 g/mol, an intrinsic viscosity [η] of0.88 dL/g, the amount of short chain branching (SCB^(f)) was 33.39CH₃/1000C and the Non-Comonomer Index value of Fraction 1 (NCI^(i)) was0.983.

The NCID_(i) of Example 6 was plotted in FIG. 12 , as well as themolecular weight distributions of eleven 3D-CFC TREF fractions andcumulative (overall) molecular weight distribution. The component Bportion of Example 6 contained intermediate branching produced by thein-line intermediate branching catalyst formulation. As shown in FIG. 12, Example 6's Non-Comonomer Index Distribution (NCID_(i)) was similar toExample 5 (FIG. 11 ); which reflected the similarity in the design ofthese two examples.

The 3D-CFC analysis of Example 7 was summarized in Table 14 and FIG. 13; and physical characteristics were summarized in Table 11. Example 7was a dual reactor ethylene/1-octene interpolymer produced in acommercial solution polymerization plant; containing about 40 wt % of acomponent A and about 60 wt % of a component B. Component A was producedin a first reactor (R1) using an unbridged single site catalystformulation and component B was produced in a second reactor (R2) usingan in-line intermediate branching catalyst formulation; R1 and R2 wereoperated in series mode. Given similar product design, the shape ofExample 7's Non-Comonomer Index Distribution (NCID), shown in FIG. 13 ,was similar relative to Examples 5 and 6 shown in FIGS. 10 and 12 ,respectively.

Table 15 and FIG. 14 summarized the 3D-CFC analysis of Comparative 6;and physical characteristics were disclosed in Table 11. Comparative 6was a multicomponent ethylene interpolymer product produced using asingle site catalyst formation in a first reactor (producing a componentA) and a comparative batch Ziegler-Natta catalyst formulation in asecond reactor (producing a component B). Comparative 6 was Elite 5100Gavailable from The Dow Chemical Company (Midland, Mich., USA). ComponentA in Comparative 6 was believed to be produced by the same single sitecatalyst formulation used to manufacture Comparative 4; further, thecomponent A portion of Example 6 contained long chain branching asevidenced by the Long Chain Branching Factor (LCBF) discussion (below).The component B portion of Comparative 6 was believed to be produced bythe same comparative batch ZN catalyst formulation used to manufactureComparatives 1 and 2; further, component B does not contain intermediatebranching as evidenced by FIGS. 1, 4 and 6 and did not contain LCB (seeLCBF discussion). As shown in Table 15, Comparative 6 was fractionatedinto nine 3D-CFC TREF fractions; fraction 1 (F1) collected from 30° C.to 55° C. was 0.1268 weight fraction (wt.fr.)¹. Fraction F1 had a weightaverage molecular weight (M_(w)) of 97,400 g/mol, a viscosity averagemolecular weight (M_(v)) of 91,100 g/mol, an intrinsic viscosity [η] of1.216 dL/g, the amount of short chain branching (SCB^(f)) was 31.02CH₃/1000C and the Non-Comonomer Index value of Fraction 1 (NCI₁) was0.950. Comparative 6's NCID_(i) plotted in FIG. 14 showed amonotonically decreasing NCID_(i).

Tables 10a and 10b summarized the solution process conditions used tomanufacture Examples 10 and 11; and the resulting physicalcharacteristics were summarized in Table 16. Example 10 was a dualreactor and dual catalyst ethylene/1-octene interpolymer productcontaining: about 50% of a component A produced in a first reactor (R1)using a bridged metallocene catalyst formulation, and; about 50% of acomponent B produced in a second reactor (R2) using an in-lineintermediate branching catalyst formulation that produced intermediatebranching. Example 10 was produced with R1 and R2 operated in seriesmode. Example 11 was a dual reactor and dual catalyst ethylene/1-octeneinterpolymer product containing: about 60% of a component A produced ina first reactor (R1) using a bridged metallocene catalyst formulation,and; about 40% of a component B produced in a second reactor (R2) usingand an in-line intermediate branching catalyst formulation that producedintermediate branching. Example 11 was manufactured with R1 and R2operated in parallel mode.

Table 17 summarized 3D-CFC analysis of Example 10. Example 10 wasfractionated into nine 3D-CFC TREF fractions; fraction 1 (1) collectedfrom 30° C. to 50° C. was 0.0812 weight fraction (wt.fr.)¹. Fraction F1had a weight average molecular weight (M_(w)) of 98,300 g/mol, aviscosity average molecular weight (M_(v)) of 93,200 g/mol, an intrinsicviscosity [TI] of 1.23 dL/g, the amount of short chain branching(SCB^(f)) was 33.60 CH₃/1000C and the Non-Comonomer Index value ofFraction 1 (NCI₁) was 0.961. The NCID_(i) of Example 10 was plotted inFIG. 15 , as well as the molecular weight distributions of nine 3D-CFCTREF fractions and cumulative (overall) molecular weight distribution.Component B in Example 10 contained intermediate branching produced byan in-line intermediate branching catalyst formulation. The shape of theNCID_(i) in FIG. 15 reflected the following facts: (1) component B'sintermediate branching reduced NCID_(i) ^(B) values monotonically asLog(Molar Mass) increased as shown in FIG. 5 and the

$\frac{{dNCID}_{i}}{d\log M_{i}}$

of component B was ≤−0.0001 as shown in FIG. 6 , and; (2) component Acontained long chain branching and had a constant NCID_(i) ^(A) and the

$\frac{{dNCID}_{i}}{d\log M_{i}}$

of component A was zero, or >−0.0001. These facts were supported by FIG.16 . FIG. 16 illustrated a simulation of Example 10 showing the NCID_(i)distribution of a binary blend of: i) 50 wt % of long chain branchedcomponent A having a constant NCID_(i) ^(A) of 0.970, and, ii) 50 wt %component B having a NCID_(i) ^(B) defined by Eq. (3), where β₀, β₁, β₂,and β₃ were 1.0100, −0.0001, 0.0001 and −0.0011, respectively, and M_(o)was 60000; component B was also characterized by

${\frac{{dNCID}_{i}}{d\log M_{i}}{values}} \leq {- {0.0001.}}$

The computer simulation was a reasonable representation of Example 10 asevidenced by the similarity between the experimentally measured NCID_(i)values (long dash curve) and the simulated NCID_(i) values (dottedcurve) in FIG. 16 .

The 3D-CFC analysis of Example 11 is summarized in Table 18 and FIG. 17. Example 11 was produced in parallel reactor mode and contained about40 wt % of a component A and about 60 wt % of a component B. The shapeof Example 11's NCID; (FIG. 17 ) reflected intermediate branching incomponent B and long chain branching in component A.

Comparatives 7 and 8 were dual reactor products produced using thesolution pilot plant (disclosed herein) employing the bridgedmetallocene catalyst formulation comprising diphenylmethylene(cyclopentadienyl) (2,7-di-t-butylfuorenyl) hafnium dimethyl in bothreactors. Similar to Comparative 5 (FIG. 9 and Table 9), the NCID_(i)values of Comparatives 7 and 8 were best represented by one parameter(i.e. the mean, 0.954 and 0.929, respectively) intercept models; thusComparative 7 and Comparative 8 had

$\frac{{dNCID}_{i}}{d\log M_{i}}$

values of zero.

Long Chain Branching Factor (LCBF)

The Long Chain Branching Factor, hereinafter LCBF, was used to quantifythe amount of Long Chain Branching (LCB) in ethylene/α-olefininterpolymers. Some embodiments of the disclosed ethylene/α-olefininterpolymer products did not contain LCB (or an undetectable level ofLCB). Other embodiments of the disclosed ethylene/α-olefin interpolymerproducts contained LCB.

LCB is a structural phenomenon in polyethylenes and well-known to thoseof ordinary skill. In this disclosure, a long chain branch was equal to,or greater than, the entanglement molecular weight, M_(e). M_(e) is awell-known concept in polymer physics (e.g. reported to be about 1kg/mol for polyethylenes, see Fetters et al., Macromolecules 1999, 32,6847). In this disclosure, long chain branches were characterized as‘rheologically active’; the term rheologically active means the presenceof long chain branches in a sample was evident after comparingrheological test results with a comparative sample that did not containlong chain branches. Non-limiting examples of rheological test resultsinclude, flow activation energy (Eact), shear thinning or viscosityratios, melt flow ratios (I₂₁/I₂, I₁₀/I₂, etc.), melt strength and longchain branching factor (LCBF), etc.

Typically, in the art, three methods have been used for LCB analysis,i.e.: nuclear magnetic resonance spectroscopy (NMR), for example see J.C. Randall, J Macromol. Sci., Rev. Macromol. Chem. Phys. 1989, 29, 201;triple detection SEC equipped with a DRI, a viscometer and a low-anglelaser light scattering detector, for example see W. W. Yau and D. R.Hill, Int. J. Polym. Anal. Charact. 1996; 2:151; and rheology, forexample see W. W. Graessley, Acc. Chem. Res. 1977, 10, 332-339.

A limitation with LCB analysis via NMR is that it cannot distinguishbranch length for branches equal to or longer than six carbon atoms(thus, NMR cannot be used to characterize LCB in ethylene/1-octenecopolymers, which have hexyl groups as side branches).

The triple detection SEC method measures the intrinsic viscosity ([q])(see W. W. Yau, D. Gillespie, Analytical and Polymer Science, TAPPIPolymers, Laminations, and Coatings Conference Proceedings, Chicago2000; 2: 699 or F. Beer, G. Capaccio, L. J. Rose, J. Appl. Polym. Sci.1999, 73: 2807 or P. M. Wood-Adams, J. M. Dealy, A. W. deGroot, O. D.Redwine, Macromolecules 2000; 33: 7489). By referencing the intrinsicviscosity of a branched polymer ([η]_(b)) to that of a linear one([η]_(i)), at the same molecular weight, the viscosity branching indexfactor g′ (g′=[η]_(b)/[η]_(i)) was used for branching characterization.However, both short chain branching (SCB) and long chain branching (LCB)make contribution to the intrinsic viscosity ([η]), effort was made toisolate the SCB contribution for ethylene/1-butene and ethylene/1-hexenecopolymers but not ethylene/1-octene copolymers (see Lue et al., U.S.Pat. No. 6,870,010). In this disclosure, a systematical investigationwas performed to look at the SCB impact on the Mark-Houwink constant Kfor three types of ethylene/1-olefin interpolymers, i.e. octene, hexeneand butene interpolymers. After correction for SCB, triple detection SECdata was used to calculate the Long Chain Branching Factor (LCBF).

In the art, rheology has been an effective method to measure the amountof LCB, or lack of, in ethylene interpolymers. Several rheologicalmethods to quantify LCB have been disclosed. One commonly-used methodwas based on zero-shear viscosity (η₀) and weight average molar mass(M_(w)) data. The 3.41 power dependence (η₀=K×M_(w) ^(3.41)) has beenestablished for monodisperse polyethylene solely composed of linearchains, for example see R. L. Arnett and C. P. Thomas, J. Phys. Chem.1980, 84, 649-652. An ethylene polymer with a no exceeding what wasexpected for a linear ethylene polymer, with the same M_(w), wasconsidered to contain long-chain branches. However, there is a debate inthe field regarding the influence of polydispersity, e.g. M_(w)/M_(o). Adependence on polydispersity was observed in some cases (see M. Ansariet al., Rheol. Acta, 2011, 5017-27) but not in others (see T. P. Karjalaet al., Journal of Applied Polymer Science 2011, 636-646).

Another example of LCB analysis via rheology was based on zero-shearviscosity (η₀) and intrinsic viscosity ([η]) data, for example see R. N.Shroff and H. Mavridis, Macromolecules 1999, 32, 8454; which isapplicable for essentially linear polyethylenes (i.e. polyethylenes withvery low levels of LCB). A limitation of this method is the contributionof the SCB to the intrinsic viscosity. It is well known that [η]decreases with increasing SCB content.

In this disclosure, a systematical investigation was performed to lookat the impact of both SCB and molar mass distribution on LCBcharacterization. After the deduction of the contribution of both SCBand molar mass distribution (polydispersity), a Long Chain BranchingFactor (LCBF) was introduced to characterize the amount of LCB inethylene/α-olefin interpolymers, as described in the followingparagraphs.

FIG. 18 illustrated the calculation of LCBF. The solid ‘Linear ReferenceLine’ shown in FIG. 18 characterized ethylene/α-olefin interpolymersthat did not contain LCB (or undetectable LCB). Ethylene/α-olefininterpolymers containing LCB deviate from this Reference Line. Forexample, Example 10 and Comparatives 4, 5 and 6 deviated horizontallyand vertically from the Reference Line.

LCBF calculation requires the polydispersity corrected Zero ShearViscosity (ZSV_(c)) and the SCB corrected Intrinsic Viscosity (IV_(c)).

The correction to the Zero Shear Viscosity, ZSV_(c), having dimensionsof poise, was performed as shown in equation Eq. (10),

$\begin{matrix}{{ZSV}_{c} = \frac{1.8389 \times \eta_{0}}{2.411^{L{n({Pd})}}}} & {{Eq}.(10)}\end{matrix}$

where η₀, the zero shear viscosity (poise), was measured by DMA asdescribed in the Testing Methods section of this disclosure; Pd was thedimensionless polydispersity (i.e. M_(w)/M_(n)) as measured usingconventional SEC (see Testing Methods) and 1.8389 and 2.4110 aredimensionless constants.

The correction to the Intrinsic Viscosity, IV₀, having dimensions ofdL/g, was performed as shown in equation Eq. (11),

$\begin{matrix}{{IV}_{c} = {\lbrack\eta\rbrack + \frac{A \times {SCB} \times M_{v}^{0.725}}{1000000}}} & {{Eq}.(11)}\end{matrix}$

where the intrinsic viscosity [q] (dL/g) was measured using 3D-SEC (seeTesting Methods); SCB having dimensions of (CH₃#/1000C) was determinedusing FTIR (see Testing Methods), and; M_(v), the viscosity averagemolar mass (g/mole), was determined using 3D-SEC (see Testing Methods).The comonomer dependent constant A was defined above. In the case of anethylene homopolymer no correction is required for the Mark-Houwinkconstant, i.e. SCB is zero.

As shown in FIG. 18 , linear ethylene/α-olefin interpolymers (which donot contain LCB or undetectable levels of LCB) fall on the ReferenceLine, e.g. Examples 1, 4 and 5 and Comparatives 1 and 3, as defined byEq. (12).

Log(IV_(c))=0.2100×Log(ZSV_(c))−0.7879  Eq.(12)

Tables 19a and 19b disclosed Reference Resins having M_(w)/M_(n) (Pd)values that ranged from 1.68 to 9.23 containing 1-octene, 1-hexene or1-butene α-olefins. Reference Resins included ethylene interpolymersproduced in solution, gas phase or slurry processes with comparativeZiegler-Natta, homogeneous and mixed (comparativeZiegler-Natta+homogeneous) catalyst formulations. Reference resins,having no LCB (or undetectable LCB), were characterized by LCBF valuesless than 0.001 (dimensionless), as supported by the LCBF valuesreported in Table 19b where LCBF values ranged from 0.000426 to1.47×10⁻⁹.

As shown in FIG. 18 , the calculation of the LCBF was based on theHorizontal-Shift (S_(h)) and Vertical-Shift (S_(v)) from the linearreference line, as defined by the following equations:

S _(h)=Log(ZSV_(c))−4.7619×Log(IV_(c))−3.7519  Eq.(13)

S _(v)=0.2100×Log(ZSV_(c))−Log(IV_(c))−0.7879  Eq.(14)

In Eq. (13) and Eq. (14), it was required that ZSV_(c) and IV_(c) havedimensions of poise and dL/g, respectively. The Horizontal-Shift (S_(h))was a shift in ZSV_(c) at constant Intrinsic Viscosity (IV_(c)), if oneremoves the Log function its physical meaning is apparent, i.e. a ratioof two Zero Shear Viscosities, the ZSV_(c) of the sample under testrelative to the ZSV_(c) of a linear ethylene polymer having the sameIV_(c). The Horizontal-Shift (S_(h)) was dimensionless. TheVertical-Shift (S_(v)) was a shift in IV_(c) at constant Zero ShearViscosity (ZSV_(c)), if one removes the Log function its physicalmeaning is apparent, i.e. a ratio of two Intrinsic Viscosities, theIV_(c) of a linear ethylene polymer having the same ZSV_(c) relative tothe IV_(c) of the sample under test. The Vertical-Shift (S_(v)) wasdimensionless.

In this disclosure a dimensionless Long Chain Branching Factor (LCBF)was defined by Eq. (15):

$\begin{matrix}{{LCBF} = \frac{S_{h} \times S_{v}}{2}} & {{Eq}.(15)}\end{matrix}$

Given the data in Table 20 the LCBF of Examples 1, 4, 5-7, 10 and 11were calculated. To be more clear: the S_(h) and S_(v) of Example 1 were−0.0487 and −0.0102, respectively, thus the LCBF was 0.000249 ((−0.0487x −0.0102)/2), i.e. Example 1 did not contain LCB; in contrast, Examples10 and 11 contained LCB given the LCBF values of 0.0291 and 0.0205,respectively.

Examples 1 and 4-7, having LCBF values less than 0.001, did not containLCB (or undetectable LCB); but did contain intermediate branching (asdiscussed above). FIG. 18 showed Examples 1, 4 and 5 falling on theReference Line defined by Eq. (12), i.e. no LCB. Examples 1 and 4 weremanufactured as disclosed in Tables 1a and 1b using embodiments of anintermediate branching catalyst formulation; physical characteristics ofExamples 1 and 4 were disclosed in Table 2.

Examples 5-7 contained two components: component A was produced in afirst reactor using an unbridged single site catalyst formulation thatproduced interpolymer that did not contain LCB or intermediatebranching, and; component B was produced in a second reactor using anin-line intermediate branching catalyst formulation that producedinterpolymer that did not contain LCB but did contain intermediatebranching. The solution process conditions required to manufactureExample 5 were summarized in Tables 10a and 10b and the physicalcharacteristics were summarized in Table 11.

As shown in Table 20, Examples 10 and 11 contained LCB as evidenced byLCBF values of 0.0291 and 0.0205, respectively; i.e. LCBF ≥0.001. FIG.18 showed the significant deviation of Example 10 from the LinearReference Line. Examples 10 and 11 contained two components: LCBcontaining component A was produced in a first reactor employing abridged metallocene catalyst formulation; and; component B was producedin a second reactor using an in-line intermediate branching catalystformulation producing an interpolymer that did not contain LCB but didcontain intermediate branching. The solution process conditions requiredto manufacture Examples 10 and 11 were summarized in Tables 10a and 10band physical characteristics were summarized in Table 16.

As shown in Table 21, Comparatives 1 and 3 did not contain LCB (LCBF was<0.001). Comparatives 1 and 3 did not contain intermediate branching.Comparative 1 was produced in a solution process using a comparativebatch Ziegler-Natta catalyst formulation, physical properties weresummarized in Table 2. Comparative 3 was produced in a solution processusing an unbridged single site catalyst formulation; physical propertieswere summarized in Table 7.

As evidenced by the LCBF values shown in Table 21, Comparatives 4through 8 contained LCB. To be more clear: Comparative 4 contained LCBas evidenced by the LCBF value of 0.0406 disclosed in Table 21 (LCBF≥0.001), as well as the significant deviation from the Linear ReferenceLine shown in FIG. 18 . Comparative 4 was an ethylene/1-octene copolymerproduced in a solution polymerization process employing a constrainedgeometry catalyst; physical characteristics were summarized in Table 7.Comparative 5 contained LCB as evidenced by the LCBF value of 0.0563.Comparative 5 was an ethylene/1-octene copolymer produced in thesolution pilot plant (disclosed herein) employing a bridged metallocenecatalyst formulation; physical characteristics were disclosed in Table7.

Comparative 6 was a competitive ethylene/1-octene interpolymer producedin a dual reactor solution process. Comparative 6 contained twocomponents: long chain branched component A was produced in a firstreactor using a constrained geometry catalyst formulation, and;component B was produced in a second reactor using a comparative batchZN catalyst formulation that produced an interpolymer that did notcontain LCB or intermediate branching. Comparative 6 contained LCB asevidenced by the LCBF value of 0.00883 disclosed in Table 21 (LCBF≥0.001). Further: component A in Comparative 6 was believed to beproduced by the same constrained geometry catalyst that was used tomanufacture Comparative 4 (Comparative 4 contained LCB), and; componentB in Comparative 6 was believed to be produced by the same comparativebatch ZN catalyst formulation used to manufacture Comparative 1(Comparative 1 did not contain LCB or intermediate branching). Thephysical characteristics of Comparative 6 were summarized in Table 11.

Comparatives 7 and 8 were dual reactor products produced using thesolution pilot plant (disclosed herein) and the same catalystformulation was employed in both reactors; more specifically, thebridged metallocene catalyst formulation, containing diphenylmethylene(cyclopentadienyl) (2,7-di-t-butylfuorenyl) hafnium dimethyl, wasinjected into both reactors 1 and 2. As shown in Table 21, Comparatives7 and 8 contained long chain branching, i.e. the dimensionless LCBF was0.0438 and 0.0541, respectively. The physical characteristics ofComparatives 7 and 8 were summarized in Table 16, these interpolymershad a melt index (12) of about 1.0 dg/min; polydispersities(M_(w)/M_(n)) were 3.32 and 2.51, respectively.

In this disclosure, resins having LCB were characterized by a LCBF of0.001 (dimensionless); and resins having no LCB (or undetectable LCB)were characterized by a LCBF of less than 0.001.

Solution Polymerization Process

Non-limiting embodiments of continuous solution polymerization processeswherein ethylene interpolymer products having intermediate branching maybe produced are shown in FIGS. 19 and 20 . These Figures are not to beconstrued as limiting, it being understood that embodiments are notlimited to the precise arrangement of, or number of, vessels shown.

Intermediate Branching Catalyst Formulations

Embodiments are described where an in-line intermediate branchingcatalyst formulation and a batch intermediate branching catalystformation were used. The term ‘in-line’ referred to the continuoussynthesis of a small quantity of catalyst and immediately injecting thiscatalyst into at least one continuously operating reactor wherein anethylene interpolymer was formed. The terms ‘batch’ referred to thesynthesis of a much larger quantity of catalyst or procatalyst in one ormore mixing vessels that are external to, or isolated from, thecontinuously operating solution polymerization process. Once prepared,the batch catalyst formulation, or batch procatalyst, was transferred toa catalyst storage tank. The term ‘procatalyst’ referred to an inactivecatalyst formulation (inactive with respect to ethylene polymerization);procatalyst was converted to an active catalyst by adding an alkylaluminum co-catalyst. As needed, the procatalyst was pumped from thestorage tank to at least one continuously operating reactor wherein anethylene interpolymer was formed. The procatalyst may be converted intoan active catalyst in the reactor or external to the reactor.

As described in the following paragraph a wide variety of chemicalcompounds can be used to synthesize an in-line intermediate branchingcatalyst formulation; it being understood that disclosed embodimentswere not limited to the specific chemical compounds disclosed.

An in-line intermediate branching catalyst formulation may be formedfrom: component (v), a magnesium compound; component (vi), a chloridecompound; component (vii), a metal compound; component (viii), an alkylaluminum co-catalyst; and component (ix), an aluminum alkyl. Anon-limiting example of an intermediate branching catalyst formulationmay be prepared as follows. In the first step, a solution of a magnesiumcompound (component (v)) was reacted with a solution of chloridecompound (component (vi)) forming a magnesium chloride support suspendedin solution. Non-limiting examples of magnesium compounds includedMg(R¹)₂; wherein the R¹ groups may be the same or different, linear,branched or cyclic hydrocarbyl radicals containing 1 to 10 carbon atoms.Non-limiting examples of chloride compounds include R²Cl; where R²represents a hydrogen atom, or a linear, branched or cyclic hydrocarbylradical containing 1 to 10 carbon atoms. In the first step, the solutionof magnesium compound may also contain an aluminum alkyl (component(ix)). Non-limiting examples of aluminum alkyl include Al(R³)₃, whereinthe R³ groups may be the same or different, linear, branched or cyclichydrocarbyl radicals containing from 1 to 10 carbon atoms. In the secondstep a solution of the metal compound (component (vii)) was added to thesolution of magnesium chloride and the metal compound was supported onthe magnesium chloride. Non-limiting examples of suitable metalcompounds included M(X)_(n) or MO(X)_(n); where M represents a metalselected from Group 4 through Group 8 of the Periodic Table, or mixturesof metals selected from Group 4 through Group 8; O represents oxygen,and; X represents chloride or bromide; n is an integer from 3 to 6 thatsatisfies the oxidation state of the metal. Additional non-limitingexamples of suitable metal compounds include Group 4 to Group 8 metalalkyls, metal alkoxides (which may be prepared by reacting a metal alkylwith an alcohol) and mixed-ligand metal compounds that contain a mixtureof halide, alkyl and alkoxide ligands. In the third step a solution ofan alkyl aluminum co-catalyst (component (viii)) was added to the metalcompound supported on the magnesium chloride. A wide variety of alkylaluminum co-catalysts were suitable, as expressed by Formula (I):

Al(R⁴)_(p)(OR⁵)_(q)(X)_(r)  (I)

wherein R⁴ groups may be the same or different, hydrocarbyl groupshaving from 1 to 10 carbon atoms; OR⁵ groups may be the same ordifferent, alkoxy or aryloxy groups wherein R⁵ is a hydrocarbyl grouphaving from 1 to 10 carbon atoms bonded to oxygen; X is chloride orbromide, and; (p+q+r)=3, with the proviso that p is greater than 0.Non-limiting examples of suitable alkyl aluminum co-catalysts includetrimethyl aluminum, triethyl aluminum, tributyl aluminum, dimethylaluminum methoxide, diethyl aluminum ethoxide, dibutyl aluminumbutoxide, dimethyl aluminum chloride or bromide, diethyl aluminumchloride or bromide, dibutyl aluminum chloride or bromide and ethylaluminum dichloride or dibromide. Further, to produce a highly activein-line intermediate branching catalyst formulation the quantity andmole ratios of components (v) through (ix) were optimized as describedbelow; where the term ‘highly active’ means the catalyst formulation wasvery efficient in converting olefins to an ethylene interpolymer havingintermediate branching, i.e. maximizing the following ratio: (pounds ofethylene interpolymer product produced) per (pounds of catalystconsumed).

In-line intermediate branching catalyst formulation synthesis may becarried out in a variety of solvents; non-limiting examples of solventsinclude linear or branched C₅ to C₁₂ alkanes or mixtures thereof.

A batch intermediate branching procatalyst may be prepared bysequentially added the following components to a stirred mixing vessel:(a) a solution of a magnesium compound (component (v)); (b) a solutionof a chloride compound (component (vi)); (c) optionally a solution of analuminum alkyl halide, and; (d) a solution of a metal compound(component (vii)). Suitable, non-limiting examples of aluminum alkylhalides are defined by the formula (R⁶)_(v)AlX_(3−v); where R⁶ groupsmay be the same or different hydrocarbyl group having from 1 to 10carbon atoms, X represents chloride or bromide, and; v is 1 or 2.Suitable, non-limiting examples of the magnesium compound, the chloridecompound and the metal compound were described earlier in thisdisclosure. Suitable solvents within which to prepare the procatalystinclude linear or branched C₅ to C₁₂ alkanes or mixtures thereof.

Individual mixing times and mixing temperatures may be used in each ofsteps (a) through (d). The upper limit on mixing temperatures for steps(a) through (d) in some case may be 160° C., in other cases 130° C. andin still other cases 100° C. The lower limit on mixing temperatures forsteps (a) through (d) in some cases may be 10° C., in other cases 20° C.and in still other cases 30° C. The upper limit on mixing time for steps(a) through (d) in some case may be 6 hours, in other cases 3 hours andin still other cases 1 hour. The lower limit on mixing times for steps(a) through (d) in some cases may be 1 minute, in other cases 10 minutesand in still other cases 30 minutes.

Batch intermediate branching procatalyst formulations can have variouscatalyst component mole ratios. The upper limit on the (chloridecompound)/(magnesium compound) molar ratio in some cases may be about 3,in other cases about 2.7 and is still other cases about 2.5; the lowerlimit in some cases may be about 2.0, in other cases about 2.1 and instill other cases about 2.2. The upper limit on the (magnesiumcompound)/(metal compound) molar ratio in some cases may be about 10, inother cases about 9 and in still other cases about 8; the lower limit insome cases may be about 5, in other cases about 6 and in still othercases about 7. The upper limit on the (aluminum alkyl halide)/(magnesiumcompound) molar ratio in some cases may be about 0.5, in other casesabout 0.4 and in still other cases about 0.3; the lower limit in somecases may be 0, in other cases about 0.1 and in still other cases about0.2. A batch intermediate branching catalyst formulation was formed whenthe procatalyst was combined with an alkyl aluminum co-catalyst.Suitable co-catalysts were described earlier in this disclosure. Theprocatalyst may be activated external to the reactor or in the reactor;in the latter case, the procatalyst and an effective amount of alkylaluminum co-catalyst were independently injected at least one reactor.

Homogeneous Catalyst Formulations

This disclosure is not limited to any specific genus of bulkyligand-metal complex; rather, a wide variety of bulky ligand-metalcomplexes may be used to form a homogeneous ethylene interpolymer thatmay comprise a portion of the ethylene interpolymer product havingintermediate branching. Homogeneous catalyst formulations produce ahomogeneous ethylene interpolymer characterized by a narrow molecularweight distribution (M_(w)/M_(n)<2.8), a narrow comonomer distribution(CDBI₅₀>70%) and devoid of intermediate branching. The followingparagraphs disclose two examples of homogeneous catalyst formulations;specifically, an unbridged single site catalyst formulation and abridged metallocene catalyst formulation; these examples are not to beconstrued as limiting.

The unbridged single site catalyst formulation employed the followingbulky ligand-metal complex Formula (II);

(L^(A))_(a)M(Pl)_(b)(Q)_(n)  (II)

wherein (L^(A)) represents a bulky ligand; M represents a metal atom; PIrepresents a phosphinimine ligand; Q represents a leaving group; a is 0or 1; b is 1 or 2; (a+b)=2; n is 1 or 2, and; the sum of (a+b+n) equalsthe valance of the metal M.

Non-limiting examples of the bulky ligand L^(A) in Formula (II) includeunsubstituted or substituted cyclopentadienyl ligands orcyclopentadienyl-type ligands, heteroatom substituted and/or heteroatomcontaining cyclopentadienyl-type ligands. Additional non-limitingexamples include, cyclopentaphenanthreneyl ligands, unsubstituted orsubstituted indenyl ligands, benzindenyl ligands, unsubstituted orsubstituted fluorenyl ligands, octahydrofluorenyl ligands,cyclooctatetraendiyl ligands, cyclopentacyclododecene ligands, azenylligands, azulene ligands, pentalene ligands, phosphoyl ligands,phosphinimine, pyrrolyl ligands, pyrozolyl ligands, carbazolyl ligands,borabenzene ligands and the like, including hydrogenated versionsthereof, for example tetrahydroindenyl ligands. In other embodiments,L^(A) may be any other ligand structure capable of q-bonding to themetal M, such embodiments include both η³-bonding and η⁵-bonding to themetal M. In other embodiments, L^(A) may comprise one or moreheteroatoms, for example, nitrogen, silicon, boron, germanium, sulfurand phosphorous, in combination with carbon atoms to form an open,acyclic, or a fused ring, or ring system, for example, aheterocyclopentadienyl ancillary ligand. Other non-limiting embodimentsfor L^(A) include bulky amides, phosphides, alkoxides, aryloxides,imides, carbolides, borollides, porphyrins, phthalocyanines, corrins andother polyazomacrocycles.

Non-limiting examples of metal M in Formula (II) include Group 4 metals,titanium, zirconium and hafnium.

The ‘leaving group’ Q in Formula (II) is any ligand that can beabstracted forming a catalyst species capable of polymerizing one ormore olefin(s). An equivalent term for Q is an ‘activatable ligand’,i.e. equivalent to the term “leaving group”. In some embodiments, Q is amonoanionic labile ligand having a sigma bond to M. Depending on theoxidation state of the metal, the value for n is 1 or 2 such thatFormula (II) represents a neutral bulky ligand-metal complex.Non-limiting examples of Q ligands include a hydrogen atom, halogens,C₁₋₂₀ hydrocarbyl radicals, C₁₋₂₀ alkoxy radicals, C₅₋₁₀ aryl oxideradicals; these radicals may be linear, branched or cyclic or furthersubstituted by halogen atoms, C₁₋₁₀ alkyl radicals, C₁₋₁₀ alkoxyradicals, C₆₋₁₀ arly or aryloxy radicals. Further non-limiting examplesof Q ligands include weak bases such as amines, phosphines, ethers,carboxylates, dienes, hydrocarbyl radicals having from 1 to 20 carbonatoms. In another embodiment, two Q ligands may form part of a fusedring or ring system.

The phosphinimine ligand, PI, is defined by Formula (III):

(RP)₃P═N—  (III)

wherein the RP groups are independently selected from: a hydrogen atom;a halogen atom; C₁₋₂₀ hydrocarbyl radicals which are unsubstituted orsubstituted with one or more halogen atom(s); a C₁₋₂₀ alkoxy radical; aC₆₋₁₀ aryl radical; a C₆₋₁₀ aryloxy radical; an amido radical; a silylradical of formula —Si(R^(s))₃, wherein the R^(s) groups areindependently selected from, a hydrogen atom, a C₁₋₈ alkyl or alkoxyradical, a C₆₋₁₀ aryl radical, a C₆₋₁₀ aryloxy radical, or a germanylradical of formula —Ge(R^(G))₃, wherein the R^(G) groups are defined asR^(s) is defined in this paragraph.

Further embodiments of Formula (II) include structural, optical orenantiomeric isomers (meso and racemic isomers) and mixtures thereof.While not to be construed as limiting, the species of Formula (II)employed in this disclosure was cyclopentadienyl tri(tertiarybutyl)phosphinimine titanium dichloride, (Cp[(t-Bu)₃PN]TiCl₂);abbreviated PIC-1 in this disclosure.

The non-limiting example of the bridged metallocene catalyst formulationemployed in this disclosure employed the following bulky ligand-metalcomplex Formula (IV);

In Formula (IV): non-limiting examples of M include Group 4 metals, i.e.titanium, zirconium and hafnium; non-limiting examples of G includeGroup 14 elements, carbon, silicon, germanium, tin and lead; Xrepresents a halogen atom, fluorine, chlorine, bromine or iodine; the R⁶groups are independently selected from a hydrogen atom, a C₁₋₂₀hydrocarbyl radical, a C₁₋₂₀ alkoxy radical or a C₆₋₁₀ aryl oxideradical (these radicals may be linear, branched or cyclic or furthersubstituted with halogen atoms, C₁₋₁₀ alkyl radicals, C₁₋₁₀ alkoxyradicals, C₆₋₁₀ aryl or aryloxy radicals); R₁ represents a hydrogenatom, a C₁₋₂₀ hydrocarbyl radical, a C₁₋₂₀ alkoxy radical, a C₆₋₁₀ aryloxide radical or alkylsilyl radicals containing at least one siliconatom and C₃₋₃₀ carbon atoms; R² and R³ are independently selected from ahydrogen atom, a C₁₋₂₀ hydrocarbyl radical, a C₁₋₂₀ alkoxy radical, aC₆₋₁₀ aryl oxide radical or alkylsilyl radicals containing at least onesilicon atom and C₃₋₃₀ carbon atoms, and; R⁴ and R⁵ are independentlyselected from a hydrogen atom, a C₁₋₂₀ hydrocarbyl radical, a C₁₋₂₀alkoxy radical a C₆₋₁₀ aryl oxide radical, or alkylsilyl radicalscontaining at least one silicon atom and C₃₋₃₀ carbon atoms.

In Formula (IV) the X(R⁶) group was a ‘leaving group’ or ‘activatableligand’; as described above in Formula (II), i.e. equivalent to thegroup Q illustrated in Formula (II).

Further embodiments of Formula (IV) include structural, optical orenantiomeric isomers (meso and racemic isomers) and mixtures thereof.While not to be construed as limiting, the species of Formula (IV)employed in this disclosure wasdiphenylmethylene(cyclopentadienyl)(2,7-di-t-butylfuorenyl)hafniumdimethyl, [(2,7-tBu₂Flu)Ph₂C(Cp)HfMe₂]; abbreviated CpF-2 in thisdisclosure.

The catalyst components required to fabricate a homogeneous catalystformulation are not particularly limited, i.e. a wide variety ofcatalyst components can be used. One non-limiting example of ahomogeneous catalyst formulation comprises the following components:component (i), a bulky ligand-metal complex; component (ii), analumoxane co-catalyst; ‘component (iii), an ionic activator; andoptionally component (iv), a hindered phenol. In this disclosure: if aspecies of Formula (II) was employed as component (i) an unbridgedsingle site catalyst formulation results; in contrast, if a species ofFormula (IV) was employed as component (i) a bridged metallocenecatalyst formulation results.

A non-limiting example of component (ii) in the homogeneous catalystformulation was an alumoxane co-catalyst that activates component (i) toa cationic complex. An equivalent term for “alumoxane” is “aluminoxane”;although the exact structure of this co-catalyst is uncertain, subjectmatter experts generally agree that it is an oligomeric species thatcontain repeating units of the general Formula (V):

(R)₂AlO—(Al(R)—O)_(n)—Al(R)₂  (V)

where the R groups may be the same or different linear, branched orcyclic hydrocarbyl radicals containing 1 to 20 carbon atoms and n isfrom 0 to about 50. A non-limiting example of an alumoxane is methylaluminoxane (or MAO) wherein each R group in formula (V) is a methylradical.

A non-limiting example of component (iii) of the homogeneous catalystformulation was an ionic activator. In general, ionic activators arecomprised of a cation and a bulky anion; wherein the latter issubstantially non-coordinating. Non-limiting examples of ionicactivators are boron ionic activators that are four coordinate with fourligands bonded to the boron atom. Non-limiting examples of boron ionicactivators include the following Formulas (VI) and (VII) shown below;

[R⁵]⁺[B(R⁷)₄ ⁻]  (VI)

where B represents a boron atom, R⁵ is an aromatic hydrocarbyl (e.g.triphenyl methyl cation) and each R⁷ is independently selected fromphenyl radicals which are unsubstituted or substituted with from 3 to 5substituents selected from fluorine atoms, C₁₋₄ alkyl or alkoxy radicalswhich are unsubstituted or substituted by fluorine atoms; and a silylradical of formula —Si(R⁹)₃, where each R⁹ is independently selectedfrom hydrogen atoms and C₁₋₄ alkyl radicals, and; compounds of Formula(VII);

[(R⁸)_(t)ZH]⁺[B(R⁷)₄]⁻  (VII)

where B is a boron atom, H is a hydrogen atom, Z is a nitrogen orphosphorus atom, t is 2 or 3 and R⁸ is selected from C₁₋₈ alkylradicals, phenyl radicals which are unsubstituted or substituted by upto three C₁₋₄ alkyl radicals, or one R^(a) taken together with thenitrogen atom may form an anilinium radical and R⁷ is as defined abovein Formula (VI).

In both Formula (VI) and (VII), a non-limiting example of R⁷ is apentafluorophenyl radical. In general, boron ionic activators may bedescribed as salts of tetra(perfluorophenyl) boron; non-limitingexamples include anilinium, carbonium, oxonium, phosphonium andsulfonium salts of tetra(perfluorophenyl)boron with anilinium and trityl(or triphenylmethylium). Additional non-limiting examples of ionicactivators include: triethylammonium tetra(phenyl)boron,tripropylammonium tetra(phenyl)boron, tri(n-butyl)ammoniumtetra(phenyl)boron, trimethylammonium tetra(p-tolyl)boron,trimethylammonium tetra(o-tolyl)boron, tributylammoniumtetra(pentafluorophenyl)boron, tripropylammoniumtetra(o,p-dimethylphenyl)boron, tributylammoniumtetra(m,m-dimethylphenyl)boron, tributylammoniumtetra(p-trifluoromethylphenyl)boron, tributylammoniumtetra(pentafluorophenyl)boron, tri(n-butyl)ammonium tetra(o-tolyl)boron,N,N-dimethylanilinium tetra(phenyl)boron, N,N-diethylaniliniumtetra(phenyl)boron, N,N-diethylanilinium tetra(phenyl)_(n)-butylboron,N,N-2,4,6-pentamethylanilinium tetra(phenyl)boron,di-(isopropyl)ammonium tetra(pentafluorophenyl)boron,dicyclohexylammonium tetra(phenyl)boron, triphenylphosphoniumtetra(phenyl)boron, tri(methylphenyl)phosphonium tetra(phenyl)boron,tri(dimethylphenyl)phosphonium tetra(phenyl)boron, tropilliumtetrakispentafluorophenyl borate, triphenylmethyliumtetrakispentafluorophenyl borate,benzene(diazonium)tetrakispentafluorophenyl borate, tropilliumtetrakis(2,3,5,6-tetrafluorophenyl)borate, triphenylmethyliumtetrakis(2,3,5,6-tetrafluorophenyl)borate, benzene(diazonium)tetrakis(3,4,5-trifluorophenyl)borate, tropilliumtetrakis(3,4,5-trifluorophenyl)borate, benzene(diazonium)tetrakis(3,4,5-trifluorophenyl)borate, tropilliumtetrakis(1,2,2-trifluoroethenyl)borate, triphenylmethyliumtetrakis(1,2,2-trifluoroethenyl)borate, benzene(diazonium)tetrakis(1,2,2-trifluoroethenyl)borate, tropilliumtetrakis(2,3,4,5-tetrafluorophenyl)borate, triphenylmethyliumtetrakis(2,3,4,5-tetrafluorophenyl)borate, and benzene(diazonium)tetrakis(2,3,4,5 tetrafluorophenyl)borate. Readily available commercialionic activators include N,N-dimethylanilinium tetrakispentafluorophenylborate, and triphenylmethylium tetrakispentafluorophenyl borate.

A non-limiting example of optional component (iv) of the homogeneouscatalyst formulation was a hindered phenol. Non-limiting example ofhindered phenols include butylated phenolic antioxidants, butylatedhydroxytoluene, 2,4-di-tertiarybutyl-6-ethyl phenol, 4,4′-methylenebis(2,6-di-tertiary-butylphenol), 1,3, 5-trimethyl-2,4,6-tris(3,5-di-tert-butyl-4-hydroxybenzyl) benzene andoctadecyl-3-(3′,5′-di-tert-butyl-4′-hydroxyphenyl) propionate.

An active homogeneous catalyst formulation was produced by optimizingthe proportion of each of the four catalyst components: component (i),component (ii), component (iii) and component (iv). In the case of onereactor (R1), the quantity of component (i) added to the reactor wasexpressed as the parts per million (ppm) of component (i) in the totalmass of reactor solution, i.e. ‘R1 (i) catalyst (ppm)’ as recited inTable 10a. The upper limit on R1 (i) catalyst (ppm) may be 5 ppm, insome cases 3 ppm and in other cases 2 ppm. The lower limit on R1 (i)catalyst (ppm) may be 0.02 ppm, in some cases 0.05 ppm and in othercases 0.1 ppm. An effective proportion of component (iii) to prepare ahomogeneous catalyst formulation was determined by optimizing the[component(iii)]/[(component (i)] molar ratio in the reactor solution,e.g. R1 (iii)/(i) as recited in Table 10a. The upper limit on R1(iii)/(i) may be 10, in some cases 5 and in other cases 2. The lowerlimit on R1 (iii)/(i) may be 0.3, in some cases 0.5 and in other cases1.0. An effective proportion of component (ii) to prepare a homogeneouscatalyst formulation was determined by optimizing the [component(ii)]/[component (i)] molar ratio, e.g. R1 (ii)/(i) as recited in Table10a. Alumoxane was generally added in a molar excess relative tocomponent (i). The upper limit on R1 (ii)/(i) may be 1000, in some cases500 and is other cases 200. The lower limit on R1 (ii)/(i) may be 1, insome cases and in other cases 30. An effective proportion of component(iv) to prepare a homogeneous catalyst formulation was determined byoptimizing the [component (iv)]/[component (ii)] molar ratio, e.g. R1(iv)/(ii) as recited in Table 10a. The upper limit on R1 (iv)/(ii) maybe 1, in some cases 0.75 and in other cases 0.5. The lower limit on R1(iv)/(ii) may be 0.0, in some cases 0.1 and in other cases 0.2.

In embodiments employing two CSTR's and two homogeneous catalystassemblies a second bridged metallocene catalyst formulation may beprepared independently of the first bridged metallocene catalystformulation and optimized as described above. Optionally, a bridgedmetallocene catalyst formulation may be employed in the tubular reactorand optimized as described above.

Embodiments in this disclosure include the use of one or morehomogeneous catalyst formulations in more than one reactor.

Solution Polymerization Process In-Line Catalyst Formulation

FIG. 19 illustrates several embodiments were two or three reactors maybe employed to produce an ethylene interpolymer product havingintermediate branching. FIG. 19 illustrates a first reactor 11 a; inthis disclosure an equivalent term for the first reactor was ‘R1’. FIG.19 also showed a second reactor 12 a; an equivalent term for the secondreactor was ‘R2’. R1 was a continuously stirred tank reactor (CSTR)agitated by stirring assembly 11 b which includes a motor external tothe reactor and an agitator within the reactor. Similarly, R2 wasagitated by stirring assembly 12 b. FIG. 19 also showed an optionaltubular reactor 17; in this disclosure, equivalent terms for the tubularreactor were ‘the third reactor’ or ‘R3’. The third reactor need not betubular, i.e. a wide variety of reactor designs may be employed. Theembodiment shown in FIG. 19 may be used to produce a first ethyleneinterpolymer in R1, a second ethylene interpolymer in R2 and a thirdethylene interpolymer in R3. Optionally, polymerization may beterminated prior to R3; in this case a third ethylene interpolymer wasnot produced. FIG. 19 illustrates an embodiment where an in-lineintermediate branching catalyst formulation was employed in R2 producinga second ethylene interpolymer having intermediate branching.Optionally, the in-line intermediate branching catalyst formulation mayalso be employed in R3 producing a third ethylene interpolymer havingintermediate branching. In an alternative embodiment, a second in-lineintermediate branching catalyst formulation may be employed in R3producing a third ethylene interpolymer having intermediate branching.In an alternative embodiment, a comparative Ziegler-Natta catalystformulation may be employed in R3 producing a third ethyleneinterpolymer that did not contain intermediate branching.

In this disclosure, a variety of catalysts may be employed in the firstreactor; for example, a homogeneous catalyst formulation, aheterogeneous catalyst formulation, a ZN catalyst formulation or anintermediate branching catalyst formulation; the latter produces a firstethylene interpolymer having intermediate branching.

Not to be construed as limiting, FIG. 19 illustrates an embodiment wherea homogeneous catalyst formulation was employed in the first reactor R1.In FIG. 19 , process solvent 1, ethylene 2 and α-olefin 3 were combinedto produce reactor feed stream RF1 which was injected into reactor 11 a,or R1. In FIG. 19 optional streams, or optional embodiments, weredenoted with dotted lines. It was not particularly important thatcombined reactor feed stream RF1 be formed; i.e. reactor feed streamscan be combined in all possible combinations, including an embodimentwhere streams 1 through 3 were independently injected into reactor 11 a.Optionally hydrogen may be injected into reactor 11 a through stream 4;hydrogen was generally added to control the molecular weight of thefirst ethylene interpolymer.

FIG. 19 illustrated an embodiment where a homogeneous catalystformulation was injected into reactor 11 a through stream 5 e.Homogeneous catalyst component streams 5 d, 5 c, 5 b and optional 5 arefer to an ionic activator (component (iii)), a bulky ligand-metalcomplex (component (i)), an alumoxane co-catalyst (component (ii)) andan optional hindered phenol (component (iv)), respectively. Homogeneouscatalyst component streams can be arranged in all possibleconfigurations, including an embodiment where streams 5 a through 5 dwere independently injected into reactor 11 a. Each homogeneous catalystcomponent was dissolved in a catalyst component solvent. Catalystcomponent solvents, for component (i) through (iv), may be the same ordifferent. Catalyst component solvents were selected such that thecombination of catalyst components did not produce a precipitate in anyprocess stream; for example, precipitation of a portion of thehomogeneous catalyst formulation in the conduit or stream 5 e. Theoptimization of the homogeneous catalyst formulation was describedbelow. Reactor 11 a produced a first exit stream, stream 11 c, thatcontained the first ethylene interpolymer dissolved in process solvent,as well as unreacted ethylene, unreacted α-olefins (if present),unreacted hydrogen (if present), active homogeneous catalyst,deactivated homogeneous catalyst, residual catalyst components and otherimpurities (if present). Melt index ranges and density ranges of thefirst ethylene interpolymer produced were described below.

FIG. 19 illustrated embodiments where reactors 11 a and 12 a can beoperated in series or parallel modes. In series mode 100% of stream 11 c(a first exit stream) passes through flow controller 11 d forming stream11 e which enters reactor 12 a. In contrast, in parallel mode 100% ofstream 11 c passes through flow controller 11 f forming stream 11 g.Stream 11 g by-passes reactor 12 a and is combined with stream 12 c (thesecond exit stream) forming stream 12 d (the third exit stream).

Fresh reactor feeds were injected into R2, reactor 12 a, i.e.; processsolvent 6, ethylene 7 and α-olefin 8 were combined to produce reactorfeed stream RF2. It was not important that stream RF2 be formed; i.e.reactor feed streams can be combined in all possible combinations,including independently injecting each stream into the reactor.Optionally hydrogen may be injected into reactor 12 a through stream 9to control the molecular weight of the second ethylene interpolymerhaving intermediate branching.

FIG. 19 illustrated an embodiment where an in-line intermediatebranching catalyst formulation (capable of producing a second ethyleneinterpolymer having intermediate branching) was injected into reactor 12a through stream 10 f. The catalyst components that comprised thein-line intermediate branching catalyst formulation were introducedthrough streams 10 a, 10 b, 10 c and 10 d; streams 10 a′, 10 b′, 10 c′represent streams containing process solvent for diluting the respectivecatalyst components and controlling stream temperatures. In thisdisclosure, the term ‘a first heterogeneous catalyst assembly’, definedby the conduits and flow controllers associated with streams 10 athrough 10 h, was operated as described in this paragraph. The firstheterogeneous catalyst assembly produced an in-line intermediatebranching catalyst formulation by optimizing feed flow rates,temperatures and the following molar ratios: (aluminum alkyl)/(magnesiumcompound) or (ix)/(v); (chloride compound)/(magnesium compound) or(vi)/(v); (alkyl aluminum co-catalyst)/(metal compound) or (viii)/(vii),and; (aluminum alkyl)/(metal compound) or (ix)/(vii); as well as thetime these compounds have to react and equilibrate. Stream 10 acontained a binary blend of a magnesium compound, component (v) and analuminum alkyl, component (ix), in process solvent. The upper limit onthe (aluminum alkyl)/(magnesium compound) molar ratio in stream 10 a maybe about 70, in some cases about 50 and is other cases about 30. Thelower limit on the (aluminum alkyl)/(magnesium compound) molar ratio maybe about 3.0, in some cases about 5.0 and in other cases about 10.Stream 10 b contained a solution of a chloride compound, component (vi),in process solvent. Stream 10 b (and associated solvent stream 10 b′)were combined with stream 10 a (and associated solvent stream 10 a′) andthe intermixing of these streams produced a magnesium chloride catalystsupport. The in-line intermediate branching catalyst formulation wasproduced by optimizing the (chloride compound)/(magnesium compound)molar ratio. The upper limit on the (chloride compound)/(magnesiumcompound) molar ratio may be about 4, in some cases about 3.5 and isother cases about 3.0. The lower limit on the (chloridecompound)/(magnesium compound) molar ratio may be about 1.0, in somecases about 1.5 and in other cases about 1.9. The time between theaddition of the chloride compound and the addition of the metal compound(component (vii)) via stream 10 c was controlled; hereafter HUT-1 (thefirst Hold-Up-Time). HUT-1 was the time for streams 10 a and 10 b toform a magnesium chloride support and equilibrate. The upper limit onHUT-1 may be about 70 seconds, in some cases about 60 seconds and isother cases about 50 seconds. The lower limit on HUT-1 may be about 5seconds, in some cases about seconds and in other cases about 20seconds. HUT-1 was controlled by adjusting the length of the conduitbetween the combination of streams 10 a and 10 b and the downstreaminjection of stream 10 c (plus 10 c′) injection, as well as controllingthe flow rates of these streams. The temperature of the solution duringHUT-1, i.e. “T^(HUT-1) ”, was controlled; the upper limit on T^(HUT-1)may be about 100° C., in some cases about 90° C. and is other casesabout 80° C.; the lower limit on T^(HUT-1) may be about 30° C., in somecases about 40° C. and in other cases about 50° C. Following HUT-1,stream 10 c containing component (vii) (and associated solvent stream 10c′) was injected into the solution containing the magnesium chloridesupport. The time between the addition of” component (vii) and theaddition of the alkyl aluminum co-catalyst, component (viii), via stream10 d was controlled; hereafter HUT-2 (the second Hold-Up-Time). HUT-2was the time for the magnesium chloride support and the component (vii)in stream 10 c to react and equilibrate. The upper limit on HUT-2 may beabout 50 seconds, in some cases about 35 seconds and is other casesabout 25 seconds. The lower limit on HUT-2 may be about 2 seconds, insome cases about 6 seconds and in other cases about seconds. HUT-2 wascontrolled by adjusting the length of the conduit between stream 10 c(plus 10 c′) injection and stream 10 d injection, as well as controllingthe flow rates of these streams. The temperature of the solution duringHUT-2, i.e. “T^(HUT-2)”, was also controlled; the upper limit onT^(HUT-2) may be about 100° C., in some cases about 90° C. and is othercases about 80° C.; the lower limit on T^(HUT-2) may be about 30° C., insome cases about 40° C. and in other cases about 50° C. The quantity ofthe alkyl aluminum co-catalyst added was optimized to produce anefficient catalyst; this was accomplished by adjusting the (alkylaluminum, co-catalyst)/(metal compound) molar ratio, or (viii)/(vii)molar ratio. The upper limit on the (alkyl aluminum co-catalyst)/(metalcompound) molar ratio may be about 10, in some cases about 7.5 and isother cases about 6.0. The lower limit on the (alkyl aluminumco-catalyst)/(metal compound) molar ratio may be 0, in some cases about1.0 and in other cases about 2.0. In addition, the time between theaddition of the alkyl aluminum co-catalyst and the injection of thein-line intermediate branching catalyst formulation into reactor 12 avia stream 10 f was controlled; hereafter HUT-3 (the thirdHold-Up-Time). HUT-3 was the time for stream 10 d to intermix andequilibrate to form the in-line intermediate branching catalystformulation. Prior to reactor injection, additional process solvent maybe added to stream 10 f via stream 10 f′. The upper limit on HUT-3 maybe about 15 seconds, in some cases about 10 seconds and is other casesabout 8 seconds. The lower limit on HUT-3 may be about 0.5 seconds, insome cases about 1 seconds and in other cases about 2 seconds. HUT-3 wascontrolled by adjusting the length of the conduit between stream 10 dinjection and the catalyst injection port on reactor 12 a, and bycontrolling the flow rates of associated streams. The R2 catalyst inlettemperature was controlled, the upper limit on R2 catalyst inlettemperature may be about 70° C., in some cases about 60° C. and is othercases about 50° C.; and the lower limit on R2 catalyst inlet temperaturemay be about 10° C., in some cases about 20° C. and in other cases about30° C. As shown in FIG. 19 , optionally, 100% of stream 10 d, the alkylaluminum co-catalyst, may be injected directly into reactor 12 a viastream 10 h. Optionally, a portion of stream 10 d may be injecteddirectly into reactor 12 a via stream 10 h and the remaining portion ofstream 10 d injected into reactor 12 a via stream 10 f. The quantity ofin-line intermediate branching catalyst formulation added to R2 isexpressed as the parts-per-million (ppm) of metal compound (component(vii)) in the reactor solution, hereafter “R2 (vii) (ppm)”. The upperlimit on R2 (vii) (ppm) may be about 10 ppm, in some cases about 8 ppmand in other cases about 6 ppm. The lower limit on R2 (vii) (ppm) insome cases may be about 0.5 ppm, in other cases about 1 ppm and in stillother cases about 2 ppm. The (aluminum alkyl)/(metal compound) molarratio in reactor 12 a, or the (ix)/(vii) molar ratio, is alsocontrolled. The upper limit on the (aluminum alkyl)/(metal compound)molar ratio in the reactor may be about 2, in some cases about 1.5 andis other cases about 1.0. The lower limit on the (aluminum alkyl)/(metalcompound) molar ratio may be about 0.05, in some cases about 0.075 andin other cases about 0.1. Any combination of the streams employed toprepare and deliver the in-line intermediate branching catalystformulation to R2 may be heated or cooled, i.e. streams 10 a through 10h (including stream 10 g (optional R3 delivery) discussed below); insome cases the upper temperature limit of streams 10 a through 10 g maybe about 90° C., in other cases about 80° C. and in still other casesabout 70° C. and; in some cases the lower temperature limit may be about10° C.; in other cases about 20° C. and in still other cases about 30°C.

As shown in FIG. 19 , if reactors 11 a and 12 a were operated in aseries mode, the second exit stream 12 c contains the second ethyleneinterpolymer having intermediate branching and the first ethyleneinterpolymer dissolved in process solvent; as well as unreactedethylene, unreacted α-olefins (if present), unreacted hydrogen (ifpresent), active catalysts, deactivated catalysts, catalyst componentsand other impurities (if present). Optionally the second exit stream 12c was deactivated by adding a catalyst deactivator A from catalystdeactivator tank 18A forming a deactivated solution A, stream 12 e; inthis case, FIG. 19 defaults to a dual reactor solution process. If thesecond exit stream 12 c was not deactivated the second exit streamenters tubular reactor 17. Catalyst deactivator A is discussed below.

If reactors 11 a and 12 a were operated in parallel mode, the secondexit stream 12 c contains the second ethylene interpolymer havingintermediate branching dissolved in process solvent. The second exitstream 12 c was combined with stream 11 g forming a third exit stream 12d, the latter contains the second ethylene interpolymer and the firstethylene interpolymer dissolved in process solvent; as well as unreactedethylene, unreacted α-olefins (if present), unreacted hydrogen (ifpresent), active catalyst, deactivated catalyst, catalyst components andother impurities (if present). Optionally the third exit stream 12 d wasdeactivated by adding catalyst deactivator A from catalyst deactivatortank 18A forming deactivated solution A, stream 12 e; in this case, FIG.19 defaults to a dual reactor solution process. If the third exit stream12 d was not deactivated the third exit stream 12 d enters tubularreactor 17.

The term “tubular reactor” was meant to convey its conventional meaning,namely a simple tube; wherein the length/diameter (L/D) ratio is atleast 10/1. Optionally, one or more of the following reactor feedstreams may be injected into tubular reactor 17; process solvent 13,ethylene 14 and optional α-olefin 15. As shown in FIG. 19 , streams 13,14 and 15 may be combined forming reactor feed stream RF3 and the latterwas injected into reactor 17. It is not particularly important thatstream RF3 be formed; i.e, reactor feed streams can be combined in allpossible combinations. Optionally hydrogen may be injected into reactor17 through stream 16. Optionally, the in-line intermediate branchingcatalyst formulation may be injected into reactor 17 via stream 10 g;i.e. a portion of the in-line intermediate branching catalystformulation enters reactor 12 a through stream 10 f and the remainingportion enters reactor 17 through stream 10 g. Although not shown inFIG. 19 , an optional process may be the injection of stream 10 gupstream of reactor 17.

FIG. 19 shows an optional embodiment where reactor 17 was supplied witha second in-line intermediate branching catalyst formulation produced ina second heterogeneous catalyst assembly. The second heterogeneouscatalyst assembly refers to the combination of conduits and flowcontrollers that include streams 34 a-34 f and 34 h. The chemicalcomposition of the first and second in-line intermediate branchingcatalyst formulations may be the same, or different. For example, thecatalyst components ((v) through (ix)) mole ratios and hold-up-times maydiffer in the first and second heterogeneous catalyst assemblies.Relative to the first heterogeneous catalyst assembly, the secondheterogeneous catalyst assembly was operated in a similar manner, i.e.the second heterogeneous catalyst assembly may be employed to produce asecond in-line intermediate branching catalyst formulation capable ofproducing a third ethylene interpolymer having intermediate branching byoptimizing feed flow rates, feed temperatures and the molar ratios ofthe catalyst components, i.e.: (aluminum alkyl)/(magnesium compound),(chloride compound)/-(magnesium compound), (alkyl aluminumco-catalyst/(metal compound, and (aluminum alkyl)/(metal compound). Tobe more clear: stream 34 a contained a binary blend of magnesiumcompound (component (v)) and aluminum alkyl (component (ix)) in processsolvent; stream 34 b contained a chloride compound (component (vi)) inprocess solvent; stream 34 c contained a metal compound (component(vii)) in process solvent; stream 34 d contained an alkyl aluminumco-catalyst (component (viii)) in process solvent; and streams stream 34a′, 34 b′, 34 c′ and 34 f′ contained process solvent. Once prepared, thesecond in-line intermediate branching catalyst formulation was injectedinto reactor 17 through stream 34 f; optionally, additional alkylaluminum co-catalyst may be injected into reactor 17 through stream 34h. As shown in FIG. 19 , optionally, 100% of stream 34 d, the alkylaluminum co-catalyst, was injected directly into reactor 17 via stream34 h. Optionally, a portion of stream 34 d was injected directly intoreactor 17 via stream 34 h and the remaining portion of stream 34 dinjected into reactor 17 via stream 34 f. In FIG. 19 , the first or thesecond heterogeneous catalyst assembly supplies 100% of the catalyst toreactor 17. Any combination of the streams that comprise the secondheterogeneous catalyst assembly may be heated or cooled, i.e. streams 34a through 34 h; in some cases, the upper temperature limit of streams 34a through 34 h may be about 90° C., in other cases about 80° C. and instill other cases about 70° C. and; in some cases the lower temperaturelimit may be about 10° C.; in other cases about 20° C. and in stillother cases about 30° C.

In reactor 17 a third ethylene interpolymer may, or may not, form. Ifembodiments of the in-line, or batch intermediate branching catalystformulations disclosed herein were employed in reactor 17, the thirdethylene interpolymer was characterized as having intermediatebranching. If a comparative Ziegler-Natta catalyst formulation wasinjected into reactor 17, the third ethylene interpolymer did notcontain intermediate branching. A third ethylene interpolymer will notform if catalyst deactivator A was added upstream of reactor 17 viacatalyst deactivator tank 18A. A third ethylene interpolymer will beformed if catalyst deactivator B is added downstream of reactor 17 viacatalyst deactivator tank 18B.

The optional third ethylene interpolymer produced in reactor 17 may beformed using a variety of operational modes; with the proviso thatcatalyst deactivator A was not added upstream of reactor 17.Non-limiting examples of operational modes include: (a) residualethylene, residual optional α-olefin and residual active catalystentering reactor 17 via stream 12 e react to form the optional thirdethylene interpolymer having intermediate branching, or; (b) a freshportion of the first in-line intermediate branching catalyst formulationwas added to reactor 17 via stream 10 g to polymerize residual ethyleneforming a third ethylene interpolymer having intermediate branching, or;(c) fresh ethylene 14, optional process solvent 13 and optional α-olefin15 were added to reactor 17 and the residual active catalyst enteringreactor 17 forms the third ethylene interpolymer having intermediatebranching, or; (d) a fresh portion of the first in-line intermediatebranching catalyst formulation was added to reactor 17 via stream 10 gto polymerize freshly injected ethylene and optional α-olefin formingthe third ethylene interpolymer having intermediate branching. Further,in operational modes (b) and (d), the first in-line intermediatebranching catalyst formulation may be replaced with a second in-lineintermediate branching catalyst formulation injected into reactor 17 viastream 34 f. In any one of these operational modes, fresh hydrogen 16may be injected into reactor 17 to reduce the molecular weight of theoptional third optional ethylene interpolymer.

In series mode, reactor 17 produced a third exit stream 17 b containingthe first ethylene interpolymer, the second ethylene interpolymer andoptionally the third ethylene interpolymer. As shown in FIG. 19 ,catalyst deactivator B may be added to the third exit stream 17 b viacatalyst deactivator tank 18B producing a deactivated solution B, stream19; with the proviso that catalyst deactivator B was not added ifcatalyst deactivator A was added upstream of reactor 17. Deactivatedsolution B may also contain unreacted ethylene, unreacted α-olefin,unreacted hydrogen and impurities if present. As indicated above, ifcatalyst deactivator A was added, deactivated solution A (stream 12 e)exits tubular reactor 17 as shown in FIG. 19 .

In parallel mode operation, reactor 17 produced a fourth exit stream 17b containing the first ethylene interpolymer, the second ethyleneinterpolymer and optionally a third ethylene interpolymer. As indicatedabove, in parallel mode, stream 12 d was the third exit stream. As shownin FIG. 19 , in parallel mode, catalyst deactivator B was added to thefourth exit stream 17 b via catalyst deactivator tank 18B producing adeactivated solution B, stream 19; with the proviso that catalystdeactivator B was not added if catalyst deactivator A was added upstreamof reactor 17.

In FIG. 19 , deactivated solution A (stream 12 e) or B (stream 19)passed through pressure let down device 20, heat exchanger 21 and apassivator was added via tank 22 forming a passivated solution 23; thepassivator was described below. The passivated solution passed throughpressure let down device 24 and entered a first vapor/liquid separator25. Hereinafter, “V/L” is equivalent to vapor/liquid. Two streams wereformed in the first V/L separator: a first bottom stream 27 comprising asolution rich in ethylene interpolymers and; a first gaseous overheadstream 26 comprising ethylene, process solvent, optional α-olefins,optional hydrogen, oligomers and light-end impurities if present.

The first bottom stream entered a second V/L separator 28. In the secondV/L separator two streams were formed: a second bottom stream 30comprising a solution that was richer in ethylene interpolymer andleaner in process solvent relative to the first bottom stream 27, and; asecond gaseous overhead stream 29 comprising process solvent, optionalα-olefins, ethylene, oligomers and light-end impurities if present.

The second bottom stream 30 flowed into a third V/L separator 31. In thethird V/L separator two streams were formed: a product stream 33comprising an ethylene interpolymer product, deactivated catalystresidues and less than 5 weight % of residual process solvent, and; athird gaseous overhead stream 32 comprised essentially of processsolvent, optional α-olefins and light-end impurities if present.

Embodiments also include the use of one or more V/L separators operatingat reduced pressure, i.e. the operating pressure is lower thanatmospheric pressure and/or embodiments where heat is added during thedevolitization process, i.e. one or more heat exchangers are employedupstream of, or within, one or more of the V/L separators. Suchembodiments facilitate the removal of residual process solvent andcomonomer such that the residual volatiles in ethylene interpolymerproducts are less than 500 ppm.

Product stream 33 proceeded to polymer recovery operations. Non-limitingexamples of polymer recovery operations included one or more gear pump,single screw extruder or twin screw extruder that forced the moltenethylene interpolymer product through a device to form pellets.Embodiments include the use of a devolatilizing extruder, where residualprocess solvent and optional α-olefin may be removed such that thevolatiles in the ethylene interpolymer product is less than 500 ppm.Once pelletized the solidified ethylene interpolymer product istypically transported to a product silo.

The first, second and third gaseous overhead streams shown in FIG. 19(streams 26, 29 and 32, respectively) may be sent to a distillationoperation where solvent, ethylene and optional α-olefin were separatedfor recycling, or; the first, second and third gaseous overhead streamsmay be recycled to the reactors, or; a portion of the first, second andthird gaseous overhead streams may be recycled to the reactors and theremaining portion sent to the distillation operation.

Solution Polymerization Process Batch Catalyst Formulation

An additional embodiment includes a process to manufacture an ethyleneinterpolymer product having intermediate branching, wherein a batchintermediate branching catalyst formulation was employed as illustratedin FIG. 20 . It being understood that the arrangement of, or number ofvessels shown in FIG. 20 are not limiting. To maintain a consistentlexicon in this disclosure CSTR reactor 112 in FIG. 20 was referred toas the second reactor, or R2, and this reactor produced a secondethylene interpolymer; and tubular reactor 117 was referred to as thethird reactor or R3 and this reactor produced an optional third ethyleneinterpolymer.

Referring to FIG. 20 : process solvent was injected into reactor 112(reactor R2) and tubular reactor 117 (reactor R3) via streams 106 and113, respectively; ethylene was injected into reactors 112 and 117 viastreams 107 and 114, respectively; α-olefin(s) were injected intoreactors 112 and 117 via streams 108 and 115, respectively; and optionalhydrogen was injected into reactors 112 and 117 via streams 109 and 116,respectively. FIG. 20 shows a reactor 112 with stirring assembly 112 b.In FIG. 20 , a first batch heterogeneous catalyst assembly, i.e. vesselsand streams 60 a through 60 e, was employed to produce a first batchintermediate branching catalyst formulation within reactor 112. Vessel60 a contained a solution or slurry of a first batch intermediatebranching procatalyst in process solvent and vessel 60 c contained asolution of alkyl aluminum co-catalyst in process solvent. A batchintermediate branching catalyst formulation or a batch intermediatebranching procatalyst formulation was injected into reactor 112 viastream 60 e and a second ethylene interpolymer having intermediatebranching was formed in reactor 112. The synthesis of an embodiment ofthe batch intermediate branching procatalyst formulation was fullydescribed below; process solvent was used to pump the batch intermediatebranching procatalyst formulation to procatalyst storage tank 60 a. Tank60 a may, or may not, be agitated. Storage tank 60 c contained an alkylaluminum co-catalyst; non-limiting examples of suitable alkyl aluminumco-catalysts were described in this disclosure. A batch intermediatebranching catalyst formulation stream 60 e was formed by mixing thebatch intermediate branching procatalyst formulation stream 60 b withalkyl aluminum co-catalyst stream 60 d; optionally, prior to reactorinjection additional process solvent may be added via stream 60 e′.Stream 60 e was injected into reactor 112 where the second ethyleneinterpolymer having intermediate branching was formed; Embodimentsinclude the following operational modes: (a) 100% of the alkyl aluminumco-catalyst was injected directly into reactor 112 through stream 60 gand the batch intermediate branching procatalyst formulation wasinjected directly into reactor 112 through stream 60 e, or; (b) aportion of the alkyl aluminum co-catalyst was injected into reactor 12 avia stream 60 g and the remaining portion passing through stream 60 dwas combined with stream 60 b to form the batch intermediate branchingcatalyst formulation in stream 60 e.

As shown in FIG. 20 , additional optional embodiments include: (a)injecting the batch intermediate branching procatalyst formulation intotubular reactor 117 through stream 60 f, or; (b) injecting the batchintermediate branching catalyst formulation into tubular reactor 117through stream 60 f. In the case of option (a), 100% of the alkylaluminum co-catalyst was injected directly into reactor 117 via stream60 h. An additional embodiment included the injection of a portion ofthe alkyl aluminum co-catalyst through stream 60 f and the remainingportion flows through stream 60 h. Any combination of vessels or streams60 a through 60 h may be heated or cooled. Employing the first batchintermediate branching catalyst formulation in reactor 117 produced athird ethylene interpolymer characterized as having intermediatebranching.

FIG. 20 illustrates further embodiments were a second heterogeneouscatalyst assembly, i.e. vessels and streams 90 a through 90 f, may beemployed. The second heterogeneous catalyst assembly allows one to:employ a second batch intermediate catalyst formulation in reactor 117to synthesize a third ethylene interpolymer having intermediatebranching; or employ a comparative batch ZN catalyst formulation inreactor 117 to synthesize a third ethylene interpolymer that does nothave intermediate branching. This disclosure also contemplates the useof a heterogeneous catalyst formulation in reactor 117 that produces athird ethylene interpolymer that does not contain intermediatebranching; for example by loading a comparative batch Ziegler-Nattacatalyst formulation into vessel 90 a.

Once prepared the second batch intermediate branching procatalyst waspumped to procatalyst storage tank 90 a using process solvent. Tank 90 amay, or may not, be agitated. Storage tank 90 c contained an alkylaluminum co-catalyst. A batch intermediate branching catalystformulation stream 90 e was formed by combining the second batchintermediate branching procatalyst stream 90 b with alkyl aluminumco-catalyst stream 90 d; optionally additional process solvent may beadded to stream 90 e via stream 90 e′. Stream 90 e was injected intoreactor 117, wherein a third ethylene interpolymer having intermediatebranching was formed. FIG. 20 includes additional embodiments where: (a)the batch intermediate branching procatalyst was injected directly intoreactor 117 through stream 90 e and the procatalyst was activated insidereactor 117 by injecting 100% of the aluminum co-catalyst directly intorector 117 via stream 90 f, or; (b) a portion of the aluminumco-catalyst flowed through stream 90 e with the remaining portionflowing through stream 90 f. Any combination of tanks or streams 90 athrough 90 f may be heated or cooled. The first and second intermediatebranching procatalyst formulations may be the same, or different.

The time between the addition of the alkyl aluminum co-catalyst and theinjection of the first batch intermediate branching catalyst formulationinto reactor 112 was controlled; i.e. HUT-4 (the fourth Hold-Up-Time).Referring to FIG. 20 , HUT-4 was the time for stream 60 d to intermixand equilibrate with stream 60 b to form the first batch intermediatebranching catalyst formulation prior to injection into reactor 112 viain stream 60 e; optionally this batch intermediate branching catalystformulation may be injected into reactor 117 via stream 60 f. The upperlimit on HUT-4 may be about 300 seconds, in some cases about 200 secondsand in other cases about 100 seconds. The lower limit on HUT-4 may beabout 0.1 seconds, in some cases about 1 seconds and in other casesabout 10 seconds. The second heterogeneous catalyst assembly wasoperated in a similar manner, i.e. the HUT-4 (time for stream 90 d tointermix and equilibrate with stream 90 b to form the second batchintermediate branching catalyst formulation prior to injection intoreactor 112 via in stream 90 e) was controlled; where HUT-4 varied fromabout 0.1 to 300 seconds.

The quantity of batch intermediate branching procatalyst formulation orbatch intermediate branching catalyst formulation added to reactor 112was expressed as ‘R2 batch (vii) (ppm)’, i.e. the parts-per-million(ppm) of metal compound, or component (vii), in the reactor solution, asshown in Table 1a. The upper limit on R2 batch (vii) may be about 10ppm, in some cases about 8 ppm and in other cases about 6 ppm. The lowerlimit on R2 batch (vii) may be about 0.1 ppm, in some cases about 0.2ppm and in other cases about 0.5 ppm. The quantity of the alkyl aluminumco-catalyst added to reactor 112 was optimized to produce an efficientcatalyst; this was accomplished by adjusting the (alkyl aluminumco-catalyst)/(metal compound) molar ratio, i.e. ‘R2 batch (viii)/(vii)(mol ratio)’ as shown in Table 1a. The upper limit on R2 batch(viii)/(vii) may be about 10, in some cases about 8.0 and is other casesabout 6.0. The lower limit on R2 batch (viii)/(vii) may be 0.5, in somecases about 0.75 and in other cases about 1.

Referring to FIG. 20 , the batch intermediate branching catalystformulation in exit stream 112 c may be deactivated upstream of reactor117 by adding a catalyst deactivator A via deactivator storage tank 118Ato form a deactivated solution A (stream 112 e); in this casedeactivated solution A exits reactor 17 and proceeds to pressure letdown device 120. Optionally, exit stream 112 c enters reactor 117 (i.e.catalyst deactivator A was not added): in this case, a wide variety ofcatalyst formulation may, or may not, be added to reactor 117 and stream117 b exits reactor 117; stream 117 b was then deactivated downstream ofreactor 117 by adding a catalyst deactivator B via deactivator storagetank 118B to form a deactivated solution B (stream 119). Deactivatedsolution B then enters pressure let down device 120. Deactivatedsolution A or B was then passed through heat exchanger 121 and apassivator was added via passivator tank 122 forming a passivatedsolution 123. The remaining vessels 124, 125, 128 and 131 and streams126, 127, 129, 130, 132 and 133 and associated process conditions havebeen described previously; to be more clear, these vessels and streamswere equivalent to vessels 24, 25, 28 and 31, respectively, and thestreams 26, 27, 29, 30, 32 and 33, respectively, described above.Ethylene interpolymer product stream 133 proceeded to polymer recoveryand was processed as described above.

The quantity of batch intermediate branching procatalyst produced and/orthe size of procatalyst storage tanks 60 a and 90a was not particularlyimportant. However, a large quantity of procatalyst allows one tooperate the continuous solution polymerization plant for an extendedperiod: the upper limit on this time in some cases may be about 3months, in other cases for about 2 months and in still other cases forabout 1 month; the lower limit on this time in some cases may be about 1day, in other cases about 1 week and in still other cases about 2 weeks.

Additional Solution Polymerization Parameters

In embodiments of the continuous solution polymerization process thatproduced an intermediately branched ethylene interpolymer a variety ofsolvents may be used as the ‘process solvent’; non-limiting examplesinclude linear, branched or cyclic C₅ to C₁₂ alkanes. Non-limitingexamples of α-olefins include 1-propene, 1-butene, 1-pentene, 1-hexene,1-octene, 1-nonene and 1-decene. Suitable catalyst component solventsinclude aliphatic and aromatic hydrocarbons. Non-limiting examples ofaliphatic catalyst component solvents include linear, branched or cyclicC₅₋₁₂ aliphatic hydrocarbons, e.g. pentane, methyl pentane, hexane,heptane, octane, cyclohexane, methylcyclohexane, hydrogenated naphtha orcombinations thereof. Non-limiting examples of aromatic catalystcomponent solvents include benzene, toluene (methylbenzene),ethylbenzene, o-xylene (1,2-dimethylbenzene), m-xylene(1,3-dimethylbenzene), p-xylene (1,4-dimethylbenzene), mixtures ofxylene isomers, hemellitene (1,2,3-trimethylbenzene), pseudocumene(1,2,4-trimethylbenzene), mesitylene (1,3,5-trimethylbenzene), mixturesof trimethylbenzene isomers, prehenitene (1,2,3,4-tetramethylbenzene),durene (1,2,3,5-tetramethylbenzene), mixtures of tetramethylbenzeneisomers, pentamethylbenzene, hexamethylbenzene and combinations thereof.

Reactor feed streams (solvent, monomer, α-olefin, hydrogen, catalystformulation etc.) must be essentially free of catalyst deactivatingpoisons; non-limiting examples of poisons include trace amounts ofoxygenates such as water, fatty acids, alcohols, ketones and aldehydes.Such poisons are removed from reactor feed streams using standardpurification practices; non-limiting examples include molecular sievebeds, alumina beds and oxygen removal catalysts for the purification ofsolvents, ethylene and α-olefins, etc.

Referring to FIGS. 19 and 20 any combination of the reactor feed streamsmay be heated or cooled: for example, reactor 11 a feed streams 1-4 (inFIG. 19 ). The upper limit on reactor feed stream temperatures may be90° C.; in other cases 80° C. and in still other cases 70° C. The lowerlimit on reactor feed stream temperatures may be 20° C.; in other cases35° C. and in still other cases 50° C. Any combination of the streamsfeeding tubular reactors 17 and 117 may be heated or cooled; i.e.streams 13-16 and 113-116, respectively. In some cases, tubular reactorfeed streams were tempered, i.e. the tubular reactor feed streams wereheated to at least above ambient temperature. The upper temperaturelimit on the tubular reactor feed streams in some cases was 200° C., inother cases 170° C. and in still other cases 140° C.; the lowertemperature limit on the tubular reactor feed streams in some cases was60° C., in other cases 90° C. and in still other cases 120° C.; with theproviso that the temperature of the tubular reactor feed streams arelower than the temperature of the process stream that enters the tubularreactor.

The operating temperature of the polymerization reactors can vary over awide range. For example, the upper limit on reactor temperatures in somecases was 300° C., in other cases 280° C. and in still other cases 260°C.; and the lower limit in some cases was 80° C., in other cases 100° C.and in still other cases 125° C. In FIG. 19 , the second reactor,reactor 12 a (R2), was operated at a higher temperature than the firstreactor 11 a (R1). The maximum temperature difference between these tworeactors (T^(R2)−T^(R1)) in some cases was 120° C., in other cases 100°C. and in still other cases 80° C.; the minimum (T^(R2)−T^(R1)) in somecases was 1° C., in other cases 5° C. and in still other cases 10° C.The optional tubular reactor, reactors 17 and 117 (also referred to asR3) in FIGS. 19 and 20 , respectively, was operated in some cases 100°C. higher than R2; in other cases 60° C. higher than R2, in still othercases 10° C. higher than R2 and in alternative cases 0° C. higher, i.e.the same temperature as R2. The temperature within optional R3 mayincrease along its length. The maximum temperature difference betweenthe inlet and outlet of R3 in some cases was 100° C., in other cases 60°C. and in still other cases 40° C. The minimum temperature differencebetween the inlet and outlet of R3 was in some cases may be 0° C., inother cases 3° C. and in still other cases 10° C. In some cases R3 wasoperated an adiabatic fashion and in other cases R3 was heated.

The pressure in the polymerization reactors should be high enough tomaintain a single phase solution and to provide the upstream pressure toforce the polymer solution from the reactors through a heat exchangerand on to polymer recovery operations. The operating pressure of thesolution polymerization reactors can vary over a wide range. Forexample, the upper limit on reactor pressure in some cases was 45 MPag,in other cases 30 MPag and in still other cases 20 MPag; and the lowerlimit in some cases was 3 MPag, in other some cases 5 MPag and in stillother cases 7 MPag. Prior to entering the first V/L separator,deactivated solution A or deactivated solution B may have a maximumtemperature in some cases of 300° C., in other cases 290° C. and instill other cases 280° C.; the minimum temperature may be in some cases150° C., in other cases 200° C. and in still other cases 220° C.Immediately prior to entering the first V/L separator, deactivatedsolution A, deactivated solution B or the passivated solution in somecases may have a maximum pressure of 40 MPag, in other cases 25 MPag andin still cases 15 MPag; the minimum pressure in some cases may be 1.5MPag, in other cases 5 MPag and in still other cases 6 MPag.

The first V/L separator (vessels 25 and 125 in FIGS. 19 and 20 ,respectively) may be operated over a relatively broad range oftemperatures and pressures. For example, the maximum operatingtemperature of the first V/L separator in some cases was 300° C., inother cases 285° C. and in still other cases 270° C.; the minimumoperating temperature in some cases was 100° C., in other cases 140° C.and in still other cases 170° C. The maximum operating pressure of thefirst V/L separator in some cases was 20 MPag, in other cases 10 MPagand in still other cases 5 MPag; the minimum operating pressure in somecases was 1 MPag, in other cases 2 MPag and in still other cases 3 MPag.

The second V/L separator (vessels 28 and 128 in FIGS. 19 and 20 ,respectively) may be operated over a relatively broad range oftemperatures and pressures. For example, the maximum operatingtemperature of the second V/L separator in some cases was 300° C., inother cases 250° C. and in still other cases 200° C.; the minimumoperating temperature in some cases was 100° C., in other cases 125° C.and in still other cases 150° C. The maximum operating pressure of thesecond V/L separator in some cases was 1000 kPag, in other cases 900kPag and in still other cases 800 kPag; the minimum operating pressurein some cases was 10 kPag, in other cases 20 kPag and in still othercases 30 kPag.

The third V/L separator (vessels 31 and 131 in FIGS. 19 and 20 ,respectively) may be operated over a relatively broad range oftemperatures and pressures. For example, the maximum operatingtemperature of the third V/L separator in some cases was 300° C., inother cases 250° C., and in still other cases 200° C.; the minimumoperating temperature in some cases may be 100° C., in other cases 125°C. and in still other cases 150° C. The maximum operating pressure ofthe third V/L separator in some cases was 500 kPag, in other cases 150kPag and in still other cases 100 kPag; the minimum operating pressurein some cases was 1 kPag, in other cases 10 kPag and in still othercases 25 kPag.

Embodiments of the continuous solution polymerization process shown inFIGS. 19 and 20 show three V/L separators. However, continuous solutionpolymerization embodiments may include configurations comprising atleast one V/L separator.

Any reactor shape or design may be used for solution polymerizationreactors, i.e. reactors 11 a (R1), 12 a (R2) and 17 (R3) in FIG. 19 ;and reactors 112 (R2) and 117 (R3) in FIG. 20 ; non-limiting examplesinclude unstirred or stirred spherical, cylindrical or tank-likevessels, as well as tubular reactors or recirculating loop reactors. Atcommercial scale the maximum volume of R1 in some cases may be about20,000 gallons (about 75,710 L), in other cases about 10,000 gallons(about 37,850 L) and in still other cases about 5,000 gallons (about18,930 L). At commercial scale the minimum volume of R1 in some casesmay be about 100 gallons (about 379 L), in other cases about 500 gallons(about 1,893 L) and in still other cases about 1,000 gallons (about3,785 L). At commercial scale the maximum volume of R2 in some cases maybe about 120,000 gallons (about 454,000 L), in other cases about 60,000gallons (about 227,000 L) and in still other cases about 30,000 gallons(about 114,000 L).

At commercial scale the minimum volume of R2 in some cases may be about6000 gallons (about 22,700 L), in other cases about 2,000 gallons (about7,570 L) and in still other cases about 200 gallons (about 757 L). Atpilot plant scales reactor volumes were typically much smaller, forexample the volume of R1 at pilot scale could be less than about 2gallons (less than about 7.6 L). In the case of continuously stirredtank reactors the stirring rate may vary over a wide range; in somecases from about 10 rpm to about 2000 rpm, in other cases from about 100to about 1500 rpm and in still other cases from about 200 to about 1300rpm. In this disclosure the volume of R3, the tubular reactor, wasexpressed as a percent of the volume of reactor R2. The upper limit onthe volume of R3 in some cases may be about 500% of R2, in other casesabout 300% of R2 and in still other cases about 100% of R2. The lowerlimit on the volume of R3 in some cases may be about 3% of R2, in othercases about 10% of R2 and in still other cases about 50% of R2.

The ‘average reactor residence time’, a well-known parameter in thechemical engineering art, was defined by the first moment of the reactorresidence time distribution; the reactor residence time distribution wasa probability distribution function that describes the amount of timethat a fluid element spends inside the reactor. The average reactorresidence time varied widely depending on process flow rates and reactormixing, design and capacity. The upper limit on the average reactorresidence time of the solution in R1 in some cases may be 600 seconds,in other cases 360 seconds and in still other cases 180 seconds. Thelower limit on the average reactor residence time of the solution in R1in some cases may be 10 seconds, in other cases 20 seconds and in stillother cases 40 seconds. The upper limit on the average reactor residencetime of the solution in R2 in some cases may be 720 seconds, in othercases 480 seconds and in still other cases 240 seconds. The lower limiton the average reactor residence time of the solution in R2 in somecases may be 10 seconds, in other cases 30 seconds and in still othercases 60 seconds. The upper limit on the average reactor residence timeof the solution in R3 in some cases may be 600 seconds, in other cases360 seconds and in still other cases 180 seconds. The lower limit on theaverage reactor residence time of the solution in R3 in some cases maybe 1 second, in other cases 5 seconds and in still other cases 10seconds.

Optionally, additional reactors (e.g. CSTRs, loops or tubes, etc.) couldbe added to the continuous solution polymerization process embodimentsshown in FIG. 19 . In this disclosure, the number of reactors was notparticularly important; with the proviso that the continuous solutionpolymerization process comprises at least one reactor that employs anintermediate branching catalyst formulation that produces an ethyleneinterpolymer product having intermediate branching.

In operating the continuous solution polymerization process embodimentsshown in FIG. 19 the total amount of ethylene supplied to the processcan be portioned or split between the three reactors R1, R2 and R3. Thisoperational variable was called the Ethylene Split (ES), i.e. “ES^(R1)”,“ES^(R2)” and “ES^(R3)” refer to the weight percent of ethylene injectedin R1, R2 and R3, respectively; with the proviso thatES^(R1)+ES^(R2)+ES^(R3)=100%. This was accomplished by adjusting theethylene flow rates in the following streams: stream 2 (R1), stream 7(R2) and stream 14 (R3). The upper limit on ES^(R1) in some cases wasabout 60%, in other cases about 55% and in still other cases about 50%;the lower limit on ES^(R1) in some cases was about 5%, in other casesabout 10% and in still other cases about 20%. The upper limit on ES^(R2)in some cases was about 90%, in other cases about 80% and in still othercases about 70%; the lower limit on ES^(R2) in some cases was about 20%,in other cases about 30% and in still other cases about 40%. The upperlimit on ES^(R3) in some cases was about 30%, in other cases about 25%and in still other cases about 20%; the lower limit on ES^(R3) in somecases was 0%, in other cases about 5% and in still other cases about10%. Similarly, in FIG. 20 the ethylene may be apportioned between R2(reactor 112) and R3 (reactor 117); where ES^(R2)+ES^(R3)=100%.

In operating the continuous solution polymerization process embodimentsshown in FIGS. 19 and 20 the ethylene concentration in each reactor wasalso controlled. The ethylene concentration in R1, i.e. EC^(R1), wasdefined as the weight of ethylene in reactor 1 divided by the totalweight of everything added to reactor 1; EC^(R2) and EC^(R3) weredefined similarly. Ethylene concentrations in the reactors (EC^(R1) orEC^(R2) or EC^(R3)) in some cases varied from about 7 weight percent (wt%) to about 25 wt %, in other cases from about 8 wt % to about 20 wt %and in still other cases from about 9 wt % to about 17 wt %.

In operating the continuous solution polymerization process embodimentsshown in FIGS. 19 and 20 the total amount of ethylene converted in eachreactor was monitored. The term ‘Q^(R1)’ referred to the percent of theethylene added to R1 that was converted into a first ethyleneinterpolymer by the catalyst formulation. Similarly, Q^(R2) and Q^(R3)represented the percent of the ethylene added to R2 and R3 that wasconverted into the second and third ethylene interpolymer, respectively.Ethylene conversions varied significantly depending on a variety ofprocess conditions, e.g. catalyst concentration, catalyst formulation,impurities and poisons. The upper limit on both Q^(R1) and Q^(R2) insome cases was about 99%, in other cases about 95% and in still othercases about 90%; the lower limit on both Q^(R1) and Q^(R2) in some caseswas about 65%, in other cases about 70% and in still other cases about75%. The upper limit on Q^(R3) in some cases was about 99%, in othercases about 95% and in still other cases about 90%; the lower limit onQ^(R3) in some cases was 0%, in other cases about 5% and in still othercases about 10%. The term “Q^(T)” represented the total or overallethylene conversion across the entire continuous solution polymerizationplant; i.e. Q^(T)=100×[weight of ethylene in the interpolymerproduct]/([weight of ethylene in the interpolymer product]+[weight ofunreacted ethylene]). The upper limit on Q^(T) in some cases was about99%, in other cases about 95% and in still other cases about 90%; thelower limit on Q^(T) in some cases was about 75%, in other cases about80% and in still other cases about 85%.

Referring to FIG. 19 , α-olefin was added to the continuous solutionpolymerization process; and was proportioned or split between R1, R2 andR3. This operational variable was called the Comonomer (α-olefin) Split(CS), i.e. ‘CS^(R1)’, ‘CS^(R2)’ and ‘CS^(R3)’ referred to the weightpercent of α-olefin comonomer that was injected in R1, R2 and R3,respectively; with the proviso that CS^(R1)+CS^(R2)+CS^(R3)=100%. Thiswas accomplished by adjusting α-olefin flow rates in the followingstreams: stream 3 (R1), stream 8 (R2) and stream 15 (R3). The upperlimit on CS^(R1) in some cases was 100% (i.e. 100% of the α-olefin wasinjected into R1), in other cases about 95% and in still other casesabout 90%. The lower limit on CS^(R1) in some cases was 0% (i.e. thefirst ethylene interpolymer was an ethylene homopolymer), in other casesabout 5% and in still other cases about 10%. The upper limit on CS^(R2)in some cases was about 100% (i.e. 100% of the α-olefin was injectedinto reactor 2), in other cases about 95% and in still other cases about90%. The lower limit on CS^(R2) in some cases was 0%, in other casesabout 5% and in still other cases about 10%. The upper limit on CS^(R3)in some cases was 100%, in other cases about 95% and in still othercases about 90%. The lower limit on CS^(R3) in some cases was 0%, inother cases about 5% and in still other cases about 10%. Similarly, inFIG. 20 the comonomer may be apportioned between R2 (reactor 112) and R3(reactor 117); where CS^(R2)+CS^(R3)=100%.

In the continuous polymerization processes described in this disclosure,polymerization was terminated by adding a catalyst deactivator.Embodiments in FIG. 19 shows catalyst deactivation occurring either: (a)upstream of tubular reactor 17 by adding a catalyst deactivator A fromcatalyst deactivator tank 18A, or; (b) downstream of tubular reactor 17by adding a catalyst deactivator B from catalyst deactivator tank 18B.Similarly, FIG. 20 shows catalyst deactivation occurring either: (a)upstream of tubular reactor 117 by adding a catalyst deactivator A fromcatalyst deactivator tank 118A, or; (b) downstream of tubular reactor117 by adding a catalyst deactivator B from catalyst deactivator tank118B. Catalyst deactivator tanks may contain neat (100%) catalystdeactivator, a solution of catalyst deactivator in a solvent, or aslurry of catalyst deactivator in a solvent. The chemical composition ofcatalyst deactivator A and B may be the same, or different. Non-limitingexamples of suitable solvents included linear or branched C₅ to C₁₂alkanes. In this disclosure, how the catalyst deactivator was added wasnot particularly important. Once added, the catalyst deactivatorsubstantially stopped the polymerization reaction by changing activecatalyst species to inactive forms. Suitable deactivators are well knownin the art, non-limiting examples include: amines (e.g. U.S. Pat. No.4,803,259 to Zboril et al.); alkali or alkaline earth metal salts ofcarboxylic acid (e.g. U.S. Pat. No. 4,105,609 to Machan et al.); water(e.g. U.S. Pat. No. 4,731,438 to Bernier et al.); hydrotalcites,alcohols and carboxylic acids (e.g. U.S. Pat. No. 4,379,882 to Miyata);or a combination thereof (U.S. Pat. No. 6,180,730 to Sibtain et al.). Inthis disclosure the quantify of catalyst deactivator added wasdetermined by the following catalyst deactivator molar ratio: 0.3(catalyst deactivator)/((total catalytic metal)+(alkyl aluminumco-catalyst)+(aluminum alkyl)) s 2.0; where the total catalytic metalwas the total moles of catalytic metal added to the solution process.The upper limit on the catalyst deactivator molar ratio was 2, in somecases 1.5 and in other cases 0.75. The lower limit on the catalystdeactivator molar ratio was 0.3, in some cases 0.35 and in still othercases 0.4. In general, the catalyst deactivator was added in a minimalamount such that the catalyst was deactivated and the polymerizationreaction was quenched.

Prior to entering the first V/L separator, a passivator or acidscavenger was added to deactivated solution A or B forming a passivatedsolution, i.e. passivated solution streams 23 and 123 shown in FIGS. 19and 20 , respectively. Passivator tanks 22 and 122 may contain neat(100%) passivator, a solution of passivator in a solvent, or a slurry ofpassivator in a solvent. Non-limiting examples of suitable solventsinclude linear or branched C₅ to C₁₂ alkanes. In this disclosure, howthe passivator was added was not particularly important. Suitablepassivators are well-known in the art, non-limiting examples includedalkali or alkaline earth metal salts of carboxylic acids orhydrotalcites. The quantity of passivator added varied over a widerange. The quantity of passivator added was determined by the totalmoles of chloride compounds added to the solution process, i.e. thechloride compound “compound (vi)” plus the metal compound “compound(vii)” that was used to manufacture the catalyst formulation. The upperlimit on the (passivator)/(total chlorides) molar ratio was 15, in somecases 13 and in other cases 11. The lower limit on the(passivator)/(total chlorides) molar ratio was about 5, in some casesabout 7 and in still other cases about 9. In general, the passivator wasadded in the minimal amount to substantially passivate the deactivatedsolution.

Ethylene Interpolymer Products

The intermediately branched ethylene interpolymer products of thisdisclosure were characterized by a Non-Comonomer Index Distribution,NCID_(i), having values characterized by Eq. (1a) and Eq. (1b), i.e. Eq.(1b) s NCID_(i)<Eq. (1a); and a first derivative of NCID_(i),dNCID_(i)/d log M_(i), Eq. (2), having values ≤−0.0001.

To maintain a consistent lexicon and avoid confusion between variousembodiments (e.g. FIGS. 19 and 20 ) the ‘second ethylene interpolymer’in the ethylene interpolymer product was consistently characterized ashaving intermediate branching. It being understood that, in the case ofone reactor running one intermediate branching catalyst formulation, theethylene interpolymer product consists of a solitary ethyleneinterpolymer, i.e. the second ethylene interpolymer having intermediatebranching.

The disclosed ethylene interpolymer products may consist of two ethyleneinterpolymers, i.e. a first and a second ethylene interpolymer where thesecond interpolymer contains intermediate branching and the firstethylene interpolymer may or may not contain intermediate branching. Thefirst ethylene interpolymer may be produced with a variety of catalystformulations; including, homogeneous catalyst formulations,heterogeneous catalyst formulations or intermediate branching catalystformulations.

The disclosed ethylene interpolymer products may consist of threeethylene interpolymers, i.e. a first, a second and a third ethyleneinterpolymer; the second ethylene interpolymer contains intermediatebranching; while the first and third ethylene interpolymers may or maynot contain intermediate branching. The first and third ethyleneinterpolymers were independently synthesized using a variety of catalystformulations; including homogeneous catalyst formulations, heterogeneouscatalyst formulations or an intermediate branching catalystformulations.

The disclosed ethylene interpolymer products may consist of more thanthree ethylene interpolymers, e.g. a first, a second, a third and afourth ethylene interpolymer (etc.); again, the second interpolymercontains intermediate branching; while the first, third and fourth(etc.) ethylene interpolymers may or may not contain intermediatebranching. The first, third and fourth (etc.) ethylene interpolymerswere independently synthesized using a variety of catalyst formulations;including homogeneous catalyst formulations, heterogeneous catalystformulations or intermediately branching catalyst formulations.

The second ethylene interpolymer was also characterized as having nolong chain branching (or an undetectable level) as characterized by aLong Chain Branching Factor (LCBF) value <0.001. The first, the third,the fourth (etc.) ethylene interpolymers may or may not contain longchain branching; if present, long chain branching was characterized by aLCBF value ≥0.001.

Ethylene interpolymer products have a density (6f); where thesuperscript ‘^(f)’ refers to the ‘final’ density, i.e. the final productmay comprise several ethylene interpolymers. In some cases, the upperlimit on density (σ^(f)) may be about 0.965 g/cm³, in other cases about0.955 g/cm³ and in still other cases about 0.945 g/cm³; while the lowerdensity limit (σ^(f)) may be about 0.862 g/cm³, in other cases about0.875 g/cm³, and; in still other cases about 0.885 g/cm³. In thisdisclosure, the symbol ‘σ²’ refers to the density of the second ethyleneinterpolymer. The lower limit on the density of the second ethyleneinterpolymer (62) may be 0.890 g/cm³, in other cases 0.900 g/cm³ and instill other cases 0.910 g/cm³; and upper limit on density of the secondethylene interpolymer may be about 0.965 g/cm³, in other cases about0.955 g/cm³ and in still other cases about 0.945 g/cm³.

The comonomer to ethylene mole ratio in the second reactor (R2) was usedto control density, i.e. ((α-olefin)/(ethylene))^(R2). The upper limiton ((α-olefin)/(ethylene))^(R2) may be about 3, in other cases about 2and in still other cases about 1; while the lower limit on((α-olefin)/(ethylene))^(R2) may be 0; in other cases about 0.25 and instill other cases about 0.5.

Ethylene interpolymer products having intermediate branching may have anupper limit on melt index (I₂ ^(f)) of about 500 dg/min, in some casesabout 400 dg/min; in other cases about 300 dg/min, and; in still othercases about 200 dg/min. The lower limit on the melt index of ethyleneinterpolymer products (I₂ ^(f)) may be about 0.3 dg/min, in some casesabout 0.4 dg/min; in other cases about 0.5 dg/min, and; in still othercases about 0.6 dg/min.

In blends the upper limit on the melt index of the second ethyleneinterpolymer (I₂ ²) having intermediate branching may be about 1000dg/min, in some cases about 750 dg/min, in other cases about 500 dg/minand in still other cases about 200 dg/min; the lower limit on the meltindex of the second ethylene interpolymer (I₂ ²) having intermediatebranching may be about 0.001 dg/min, in some cases about 0.005 dg/min,in other cases about 0.01 dg/min and in still other cases about 0.05dg/min. The hydrogen content in R2 was used to control melt index of thesecond ethylene interpolymer, i.e. H₂ ^(R2) (ppm); H₂ ^(R2) (ppm) mayrange from about 50 ppm to 0 ppm, in other cases from about 25 ppm to 0ppm, in still other cases from about 10 to 0 and or from about 2 ppm to0 ppm.

Methods to determine the CDBI₅₀ (Composition Distribution BranchingIndex) of an ethylene interpolymer are well known to those skilled inthe art. The CDBI₅₀, expressed as a percent, is defined as the percentof the ethylene interpolymer whose comonomer composition is within 50%of the median comonomer composition. Ethylene interpolymer productshaving intermediate branching may have an upper limit on CDBI₅₀ of about98%, in other cases about 90% and in still other cases about 85%; whilethe lower limit on the CDBI₅₀ of an ethylene interpolymer product may beabout 10%, in other cases about 15% and in still other cases about 20%.The second ethylene interpolymer having intermediate branching may havea CDBI₅₀ that ranges from: an upper CDBI₅₀ limit of about 70%, in othercases about 65% and in still other cases about 60%; and a lower CDBI₅₀limit of about 20%, in other cases about 45% and in still other casesabout 55%.

The upper limit on the M_(w)/M_(n) of the ethylene interpolymer producthaving intermediate branching may be about 25, in other cases about 15and in still other cases about 9. The lower limit on the M_(w)/M_(n) ofthe ethylene interpolymer product may be 2.0, in other cases about 2.2and in still other cases about 2.4. The M_(w)/M_(n) of second ethyleneinterpolymer having intermediate branching may be characterized by: anupper M_(w)/M_(n) limit of about 5.0, in other cases about 4.5 and instill other cases about 4.0; and a lower M_(w)/M_(n) limit of about 2.2,in other cases about 2.4 and in still other cases about 2.6.

In the case of ethylene interpolymer products containing more than oneethylene interpolymer; the upper limit on the weight percent (wt %) ofthe second ethylene interpolymer having intermediate branching in theethylene interpolymer product may be about 99 wt %, in other cases about95 wt % and in still other cases about 90 wt %. The lower limit on thewt % of the second ethylene interpolymer in the ethylene interpolymerproduct may be about 10 wt %; in other cases about 15 wt % and in stillother cases about 20 wt %. The specific volume blending rule was used tocalculate the final density (σ_(f)) of a multicomponent ethyleneinterpolymer product; e.g. in the case of a blend of two ethyleneinterpolymers the final blend density (σ^(f)) wasσ^(f)=1/(wt¹/σ¹+wt²/σ2); where wt¹ and wt² represent weight fractions ofthe first and second ethylene interpolymer, respectively, and thefollowing melt index blending rule was used to the calculate blend meltindex, log(I₂ ^(f)) wt¹ log(I₂ ¹)+wt² log(I₂ ²).

Ethylene interpolymer products containing intermediate branching containcatalyst residues that reflect the chemical compositions of the catalystformulation used. In the case of the second ethylene interpolymer havingintermediate branching, catalyst residues were quantified by the partsper million of catalytic metal originating from ‘component (vii)’ in thesecond ethylene interpolymer; in this disclosure this metal was referredto as “metal B”. Non-limiting examples of metal B include metalsselected from Group 4 through Group 8 of the Periodic Table, or mixturesof metals selected from Group 4 through Group 8. The upper limit on theppm of metal B in the second ethylene interpolymer having intermediatebranching may be about 12 ppm, in other cases about 10 ppm and in stillother cases about 8 ppm. The lower limit on the ppm of metal B in theethylene interpolymer having intermediate branching may be about 0.5ppm, in other cases about 1 ppm and in still other cases about 2 ppm.

The ethylene interpolymer product may also contain (optionally)additional catalytic metals. For example, as described below, a metal Aused to synthesize a first ethylene interpolymer and/or a metal C usedto synthesize a third ethylene interpolymer. Catalytic metals A, B and Cmay be the same or different. In this disclosure the term “totalcatalytic metal” was equivalent to the sum of catalytic metals A+B+C.The upper and lower limits on catalytic metal A, or metal B or metal Cin the ethylene interpolymer product can be calculated from the weightfractions of the first, the second and the third ethylene interpolymer,respectively, in the ethylene interpolymer product; given the disclosedupper and lower limits on the respective catalytic metal in the first,second and third ethylene interpolymer.

First Ethylene Interpolymer

In this disclosure, the term ‘first ethylene interpolymer’ refers to anethylene interpolymer synthesized in a first reactor. This disclosuredescribed several embodiments of intermediately branched ethyleneinterpolymer products; and the first ethylene interpolymer may, or maynot, be present in the product. If present, the first ethyleneinterpolymer may be an intermediately branched ethylene interpolymer andcharacterized as described above (e.g. via Eq. (1a), Eq. (1b) and Eq.(2), etc.). If present, the first ethylene interpolymer may also beproduced using a heterogeneous catalyst formulation, e.g. a comparativebatch Ziegler-Natta catalyst formulation that does not produceintermediate branching. If present, the first ethylene interpolymer mayalso be produced using a homogeneous catalyst formulation that does notproduce intermediate branching and may, or may not, produce long chainbranching.

The first ethylene interpolymer may have an upper density limit of about0.975 g/cm³, in other cases about 0.965 g/cm³ and in still other casesabout 0.955 g/cm³; while the lower density may be about 0.855 g/cm³, inother cases about 0.865 g/cm³, and; in still other cases about 0.875g/cm³. In this disclosure the symbol ‘a’ refers to the density of thefirst ethylene interpolymer. The ((α-olefin)/(ethylene)) ratio in thefirst reactor (R1) was used to control the density of the first ethyleneinterpolymer.

The upper limit on the melt index of the first ethylene interpolymer,(I₂ ¹) may be about 1000 dg/min, in some cases about 750 dg/min; inother cases about 500 dg/min, and; in still other cases about 200dg/min; and the lower limit on the melt index of the homogeneous firstethylene interpolymer may be about 0.001 dg/min, in some cases about0.005 dg/min; in other cases about 0.01 dg/min, and; in still othercases about 0.05 dg/min. The melt index of the first ethyleneinterpolymer was controlled by the amount of hydrogen in R1, i.e. H₂^(R1) (ppm).

The first ethylene interpolymer may, or may not, contain long chainbranching as characterized by LCBF values. The upper limit on the LCBFof the first ethylene interpolymer may be 0.5, in other cases 0.4 and instill other cases 0.3 (dimensionless). The lower limit on LCBF was ahomogenous first ethylene interpolymer that did not chain long chainbranching or an undetectable level of long chain branching, ascharacterized by LCBF values <0.001.

The first ethylene interpolymer may have a CDBI₅₀ that ranges from: anupper CDBI₅₀ of about 98%, in other cases 95% and in still other casesabout 90%; and a lower CDBI₅₀ of about 20%, in other cases about 45% andin still other cases about 55%.

The upper limit on the M_(w)/M_(n) of the first ethylene interpolymermay be about 5.0, in other cases about 4.5 and in still other casesabout 4.0; and the lower limit on the M_(w)/M_(n) the first ethyleneinterpolymer may be about 1.7, in other cases about 1.8 and in stillother cases about 1.9.

The first ethylene interpolymer contains catalyst residues that reflectthe chemical composition of the catalyst formulation used. Catalystresidues were quantified by the parts per million of catalytic metal inthe first ethylene interpolymer; hereinafter ‘metal A’. Non-limitingexamples of metal A include metals selected from Group 4 through Group 8of the Periodic Table, or mixtures of metals selected from Group 4through Group 8. The upper limit on the ppm of metal A in the firstethylene interpolymer may be about 12.0 ppm, in other cases about 10.0ppm and in still other cases about 8.0 ppm. The lower limit on the ppmof metal A in the first ethylene interpolymer may be about 0.01 ppm, inother cases about 0.1 ppm and in still other cases about 0.2 ppm.

The upper limit on the weight percent (wt %) of the first ethyleneinterpolymer in the ethylene interpolymer product may be about 60 wt %,in other cases about 55 wt % and in still other cases about 50 wt %. Thelower limit on the wt % of the first ethylene interpolymer in theethylene interpolymer product may be 0 wt %; in other cases about 5 wt %and in still other cases about 10 wt %.

Third Ethylene Interpolymer

In this disclosure, the term ‘third ethylene interpolymer’ refers to anethylene interpolymer synthesized in a third reactor. This disclosuredescribed several embodiments of intermediately branched ethyleneinterpolymer products; and the third ethylene interpolymer may, or maynot, be present. If present, the third ethylene interpolymer may be anintermediately branched ethylene interpolymer and characterized asdescribed above (e.g. via Eq. (1a), Eq. (1b) and Eq. (2), etc.). Ifpresent, the third ethylene interpolymer may also be produced using aheterogeneous catalyst formulation, e.g. a comparative batchZiegler-Natta catalyst formulation that does not produce intermediatebranching. If present, the third ethylene interpolymer may also beproduced using a homogeneous catalyst formulation that does not produceintermediate branching and may, or may not, produced long chainbranching.

The upper limit on the density (as) of the third ethylene interpolymerin some cases may be about 0.975 g/cm³, in other cases about 0.965 g/cm³and in still other cases about 0.955 g/cm³; while the lower 3 limit maybe about 0.855 g/cm³, in other cases about 0.865 g/cm³, and in stillother cases about 0.875 g/cm³.

The amount of hydrogen added to the third reactor (R3), H₂ ^(R3) (ppm),may vary over a wide range to produce a third ethylene interpolymerhaving a wide range of melt indexes (123). The upper limit on 123 may beabout 10000 dg/min, in other cases about 5000 dg/min, in still casesabout 2000 dg/min, and in other cases about 1000 dg/min; while the lowerlimit on 123 may be about 0.1 dg/min, in other cases about 0.2 dg/min,in still other cases about 0.3 dg/min, and in other cases 0.5 dg/min.

The upper limit on the CDBI₅₀ of the third ethylene interpolymer may beabout 98%, in other cases about 95% and in still other cases about 90%;while the lower limit on CDBI₅₀ of the third ethylene interpolymer maybe about 20%, in other cases about 30% and in still other cases about40%.

The upper limit on the M_(w)/M_(n) of the third ethylene interpolymermay be about 6.0, in other cases about 5.0 and in still other casesabout 4.0. The lower limit on the M_(w)/M_(n) of the third ethyleneinterpolymer may be about 1.7, in other cases about 1.8 and in stillother cases about 1.9.

The catalyst residues in the third ethylene interpolymer reflect thechemical composition of catalyst formulation used. In this disclosure,the term ‘metal C’ refers to the catalytic metal employed in thecatalyst formulation that was used to synthesize the third ethyleneinterpolymer. Non-limiting examples of metal C include metals selectedfrom Group 4 through Group 8 of the Periodic Table, or mixtures ofmetals selected from Group 4 through Group 8. Metal C was may be thesame or different relative to metal A and metal B. The upper limit onthe ppm of metal C in the third ethylene interpolymer may be about 12ppm, in other cases about 10 ppm and in still other cases about 8 ppm;and the lower limit on the ppm of metal C in the third ethyleneinterpolymer may be about 0.01 ppm, in other cases about 0.1 ppm and instill other cases about 0.2 ppm.

The upper limit on the weight percent (wt %) of the optional thirdethylene interpolymer in the ethylene interpolymer product may be about30 wt %, in other cases about 25 wt % and in still other cases about 20wt %. The lower limit on the wt % of the optional third ethyleneinterpolymer in the ethylene interpolymer product may be 0 wt %; inother cases about 5 wt % and in still other cases about 10 wt %.

Manufactured Articles

Ethylene interpolymer products having intermediate branching may beconverted into a wide variety of flexible manufactured articles.Non-limiting examples include monolayer or multilayer films.Non-limiting examples of processes to prepare such films include blownfilm processes, double bubble processes, triple bubble processes, castfilm processes, tenter frame processes and machine direction orientation(MDO) processes.

In the blown film extrusion process an extruder heats, melts, mixes andconveys a thermoplastic, or a thermoplastic blend. Once molten, thethermoplastic is forced through an annular die to produce athermoplastic tube. In the case of co-extrusion, multiple extruders areemployed to produce a multilayer thermoplastic tube. The temperature ofthe extrusion process is primarily determined by the thermoplastic orthermoplastic blend being processed, for example the melting temperatureor glass transition temperature of the thermoplastic and the desiredviscosity of the melt. In the case of polyolefins, typical extrusiontemperatures are from 330° F. to 550° F. (166° C. to 288° C.). Upon exitfrom the annular die, the thermoplastic tube is inflated with air,cooled, solidified and pulled through a pair of nip rollers. Due to airinflation, the tube increases in diameter forming a bubble of desiredsize. Due to the pulling action of the nip rollers the bubble isstretched in the machine direction. Thus, the bubble is stretched in twodirections: the transverse direction (TD) where the inflating airincreases the diameter of the bubble; and the machine direction (MD)where the nip rollers stretch the bubble. As a result, the physicalproperties of blown films are typically anisotropic, i.e. the physicalproperties differ in the MD and TD directions; for example, film tearstrength and tensile properties typically differ in the MD and TD. Insome prior art documents, the terms “cross direction” or “CD” is used;these terms are equivalent to the terms “transverse direction” or “TD”used in this disclosure. In the blown film process, air is also blown onthe external bubble circumference to cool the thermoplastic as it exitsthe annular die. The final width of the film is determined bycontrolling the inflating air or the internal bubble pressure; in otherwords, increasing or decreasing bubble diameter. Film thickness iscontrolled primarily by increasing or decreasing the speed of the niprollers to control the draw-down rate. After exiting the nip rollers,the bubble or tube is collapsed and may be slit in the machine directionthus creating sheeting. Each sheet may be wound into a roll of film.Each roll may be further slit to create film of the desired width. Eachroll of film is further processed into a variety of consumer products asdescribed below.

The cast film process is similar in that a single or multipleextruder(s) may be used; however, the various thermoplastic materialsare metered into a flat die and extruded into a monolayer or multilayersheet, rather than a tube. In the cast film process the extruded sheetis solidified on a chill roll.

In the double bubble process a first blown film bubble is formed andcooled, then the first bubble is heated and re-inflated forming a secondblown film bubble, which is subsequently cooled. The ethyleneinterpolymer products, disclosed herein, are also suitable for thetriple bubble blown process. Additional film converting processes,suitable for the disclosed ethylene interpolymer products, includeprocesses that involve a Machine Direction Orientation (MDO) step; forexample, blowing a film or casting a film, quenching the film and thensubjecting the film tube or film sheet to a MDO process at any stretchratio. Additionally, the ethylene interpolymer product films disclosedherein are suitable for use in tenter frame processes as well as otherprocesses that introduce biaxial orientation.

Depending on the end-use application, the disclosed ethyleneinterpolymer products having intermediate branching may be convertedinto films that span a wide range of thicknesses. Non-limiting examplesinclude, food packaging films where thicknesses may range from about 0.5mil (13 μm) to about 4 mil (102 μm), and; in heavy duty sackapplications film thickness may range from about 2 mil (51 μm) to about10 mil (254 μm).

Intermediately branched ethylene interpolymer products may be used inmonolayer films; where the monolayer comprises one or more of thedisclosed ethylene interpolymer products having intermediate branchingand optionally one or more ethylene polymers and/or one or morepolyolefins. The lower limit on the weight percent of intermediatelybranched ethylene interpolymer product in a monolayer film may be about3 wt %, in other cases about 10 wt % and in still other cases about 30wt %. The upper limit on the weight percent of the intermediatelybranched ethylene interpolymer product in the monolayer film may be 100wt %, in other cases about 90 wt % and in still other cases about 70 wt%.

Intermediately branched ethylene interpolymer products may also be usedin one or more layers of a multilayer film; non-limiting examples ofmultilayer films include two, three, five, seven, nine, eleven or morelayers. The disclosed ethylene interpolymer products are also suitablefor use in processes that employ micro-layering dies and/or feedblocks,such processes can produce films having many layers, non-limitingexamples include from 10 to 10,000 layers.

The thickness of a specific layer (containing one or more intermediatelybranched ethylene interpolymer product(s)) within the multilayer filmmay be about 5%, in other cases about 15% and in still other cases about30% of the total multilayer film thickness. In other embodiments, thethickness of a specific layer (containing one or more intermediatelybranched ethylene interpolymer product(s)) within the multilayer filmmay be about 95%, in other cases about 80% and in still other casesabout 65% of the total multilayer film thickness. Each individual layerof a multilayer film may contain more than one intermediately branchedethylene interpolymer product; may contain one or more ethylene polymerand/or one or more polyolefin.

Additional embodiments include laminations and coatings, where mono ormultilayer films containing an ethylene interpolymer product havingintermediate branching are extrusion laminated or adhesively laminatedor extrusion coated. In extrusion lamination or adhesive lamination, twoor more substrates are bonded together with a thermoplastic or anadhesive, respectively. In extrusion coating, a thermoplastic is appliedto the surface of a substrate. These processes are well known to thoseof ordinary experience in the art. Frequently, adhesive lamination orextrusion lamination are used to bond dissimilar materials, non-limitingexamples include the bonding of a paper web to a thermoplastic web, orthe bonding of an aluminum foil containing web to a thermoplastic web,or the bonding of two thermoplastic webs that are chemicallyincompatible, e.g. the bonding of an intermediately branched ethyleneinterpolymer product containing web to a polyester or polyamide web.Prior to lamination, the web containing intermediately branched ethyleneinterpolymer product(s) may be monolayer or multilayer. Prior tolamination the individual webs may be surface treated to improve thebonding, a non-limiting example of a surface treatment is coronatreating. A primary web or film may be laminated on its upper surface,its lower surface, or both its upper and lower surfaces with a secondaryweb. A secondary web and a tertiary web could be laminated to theprimary web; wherein the secondary and tertiary webs differ in chemicalcomposition. As non-limiting examples, secondary or tertiary webs mayinclude; polyamide, polyester and polypropylene, or webs containingbarrier resin layers such as EVOH. Such webs may also contain a vapordeposited barrier layer; for example a thin silicon oxide (SiO_(x)) oraluminum oxide (AlO_(x)) layer. Multilayer webs (or films) may containthree, five, seven, nine, eleven or more layers.

Ethylene interpolymer products having intermediate branching can be usedin a wide range of manufactured articles comprising one or more films(monolayer or multilayer). Non-limiting examples of such manufacturedarticles include: food packaging films (fresh and frozen foods, liquidsand granular foods), stand-up pouches, retortable packaging andbag-in-box packaging; barrier films (oxygen, moisture, aroma, oil, etc.)and modified atmosphere packaging; light and heavy duty shrink films andwraps, collation shrink film, pallet shrink film, shrink bags, shrinkbundling and shrink shrouds; light and heavy duty stretch films, handstretch wrap, machine stretch wrap and stretch hood films; high clarityfilms; heavy-duty sacks; household wrap, overwrap films and sandwichbags; industrial and institutional films, trash bags, can liners,magazine overwrap, newspaper bags, mail bags, sacks and envelopes,bubble wrap, carpet film, furniture bags, garment bags, coin bags, autopanel films; medical applications such as gowns, draping and surgicalgarb; construction films and sheeting, asphalt films, insulation bags,masking film, landscaping film and bags; geomembrane liners formunicipal waste disposal and mining applications; batch inclusion bags;agricultural films, mulch film and green house films; in-storepackaging, self-service bags, boutique bags, grocery bags, carry-outsacks and t-shirt bags; oriented films, machine direction and biaxiallyoriented films and functional film layers in oriented polypropylene(OPP) films, e.g., sealant and/or toughness layers. Additionalmanufactured articles comprising one or more films containing at leastone ethylene interpolymer product having intermediate branching includelaminates and/or multilayer films; sealants and tie layers in multilayerfilms and composites; laminations with paper; aluminum foil laminates orlaminates containing vacuum deposited aluminum; polyamide laminates;polyester laminates; extrusion coated laminates, and; hot-melt adhesiveformulations. The manufactured articles summarized in this paragraphcontain at least one film (monolayer or multilayer) comprising at leastone embodiment of the disclosed intermediately branched ethyleneinterpolymer products.

Intermediately branched ethylene interpolymer product have performanceattributes that are advantageous in many flexible applications. Theperformance attribute(s) required depends on how the film will be used,i.e., the specific film application the film is employed in. Ethyleneinterpolymer products having intermediate branching have a desirablebalance of properties. Elaborating, relative to competitivepolyethylenes of similar density and melt index, intermediately branchedethylene interpolymers have one or more of: improved dart impact;improved machine direction tensile strength; improved transversedirection tensile strength; improved a 45° gloss; and/or improved haze;relative to a comparative film. To be more clear: in the comparativefilm the second ethylene interpolymer having intermediate branching hasbeen replaced with a comparative second ethylene interpolymer that doesnot contain intermediate branching. The improvements in film propertiesdisclosed are not to be construed as limiting.

The films and/or flexible articles described above may optionallyinclude, depending on its intended use, additives and adjuvants.Non-limiting examples of additives and adjuvants include, anti-blockingagents, antioxidants, heat stabilizers, slip agents, processing aids,anti-static additives, colorants, dyes, filler materials, lightstabilizers, light absorbers, lubricants, pigments, plasticizers,nucleating agents and combinations thereof. Non-limiting examples ofsuitable primary antioxidants include Irganox 1010 [CAS Reg. No.6683-19-8] and Irganox 1076 [CAS Reg. No. 2082-79-3]; both availablefrom BASF Corporation, Florham Park, N.J., U.S.A. Non-limiting examplesof suitable secondary antioxidants include Irgafos 168 [CAS Reg. No.31570-04-4], available from BASF Corporation, Florham Park, N.J.,U.S.A.; Weston 705 [CAS Reg. No. 939402-02-5], available from Addivant,Danbury Conn., U.S.A. and; Doverphos Igp-11 [CAS Reg. No. 1227937-46-3]available form Dover Chemical Corporation, Dover Ohio, U.S.A.

Intermediately branched ethylene interpolymer products may also beconverted into a wide variety of rigid manufactured articles,non-limiting examples include: deli containers, margarine tubs, drinkcups and produce trays, bottle cap liners and bottle caps (forcarbonated or non-carbonated fluids), closures (including closures withliving hinge functionality), household and industrial containers, cups,bottles, pails, crates, tanks, drums, bumpers, lids, industrial bulkcontainers, industrial vessels, material handling containers, toys,bins, playground equipment, recreational equipment, boats, marineequipment, safety equipment (helmets), wire and cable applications suchas power cables, communication cables and conduits, flexible tubing andhoses, pipe applications including both pressure pipe and non-pressurepipe markets (e.g., natural gas distribution, water mains, interiorplumbing, storm sewer, sanitary sewer, corrugated pipes and conduit),foamed articles manufactured from foamed sheet or bun foam, militarypackaging (equipment and ready meals), personal care packaging, diapersand sanitary products, cosmetic/pharmaceutical/medical packaging, truckbed liners, pallets and automotive dunnage.

The rigid manufactured articles summarized above contain one or moreintermediately branched ethylene interpolymer product or a blend of atleast one intermediately branched ethylene interpolymer product with atleast one other thermoplastic. Further, the rigid manufactured articlessummarized above may be multilayer, comprising at least one layercomprising one or more ethylene interpolymer product having intermediatebranching or a blend of at least one ethylene interpolymer producthaving intermediate branching with at least one other thermoplastic.Such rigid manufactured articles may be fabricated using the followingnon-limiting processes: injection molding, compression molding, blowmolding, rotomolding, profile extrusion, pipe extrusion, sheetthermoforming and foaming processes employing chemical or physicalblowing agents.

The rigid articles described above may optionally include, depending onits intended use, additives and adjuvants. Non-limiting examples ofadditives and adjuvants include, antioxidants, slip agents, processingaids, anti-static additives, colorants, dyes, filler materials, heatstabilizers, light stabilizers, light absorbers, lubricants, pigments,plasticizers, nucleating agents and combinations thereof.

Examples

Polymerization

The following examples are presented for the purpose of illustratingembodiments of this disclosure; it being understood, that the examplespresented do not limit the claims presented.

In-Line Intermediate Branching Catalyst Formulation

Embodiments of ethylene interpolymer products having intermediatebranching were prepared in a pilot plant using an intermediate branchingcatalyst formulation.

Methylpentane was used as the process solvent (a commercial blend ofmethylpentane isomers). The volume of the first CSTR reactor (R1) was3.2 gallons (12 L), the volume of the second CSTR reactor (R2) was 5.8gallons (22 L) and the volume of the tubular reactor (R3) was 0.58gallons (2.2 L) or 4.8 gallons (18 L). The R1 pressure ranged from about14 MPa to about 18 MPa; R2 was operated at a lower pressure tofacilitate continuous flow from R1 to R2. In some embodiments R1, R2 andR3 were operated in series mode; wherein the first exit stream from R1flows directly into R2. In other embodiments R1 and R2 were operated inparallel mode; wherein the first exit from R1 and the second exit streamfrom R2 are combined downstream of R2. R2 was agitated such that thereactor contents were well mixed; R1 was agitated if this reactor wasutilized. Polymerization was conducted by continuously feeding freshprocess solvent, ethylene, 1-octene and hydrogen to the reactor orreactors.

The solution process conditions employed to manufacture Examples 1 and 4were summarized in Tables 1a and 1b. In Examples 1 an embodiment of thein-line intermediate branching catalyst formulation was injected intothe second CSTR reactor (R2); in a similar manner, Example 2 wassynthesized using the same in-line intermediate branching catalystsystem. In Example 1, 80% of the ethylene was injected into R2 (i.e. theethylene split (ES^(R2)) was 80% and the remaining ethylene was injectedin the tubular third reactor (R3) (ES^(R3) 20%). In Example 2, ES^(R2)was 100%. Example 4 was produced by injecting a batch intermediatebranching catalyst formulation into R2 and ES^(R2) was 100%. In Examples1, 2 and 4 all the comonomer (1-octene) was injected into R2, i.e. thecomonomer split, CS^(R2), was 100%. The physical and molecularcharacteristics of Examples 1, 2 and 4 were summarized in Table 2.

In the case of Examples 1 and 2, embodiments of the in-line intermediatebranching catalyst formulation were prepared from the followingcomponents: component (v), butyl ethyl magnesium; component (vi),tertiary butyl chloride; component (vii), titanium tetrachloride;component (viii), diethyl aluminum ethoxide, and; component (ix),triethyl aluminum. In step one, a solution of triethylaluminum anddibutylmagnesium ((triethylaluminum)/(dibutylmagnesium) molar ratio of20) was combined with a solution of tertiary butyl chloride and allowedto react for about 30 seconds (HUT-1); in step two, a solution oftitanium tetrachloride was added to the mixture formed in step one andallowed to react for about 14 seconds (HUT-2), and; in step three, themixture formed in step two was allowed to reactor for an additional 3seconds (HUT-3) prior to injection into R2. The average solutiontemperature during HUT-1, T^(HUT-1) was 65.3° C.; and the averagesolution temperature during HUT-2, T^(HUT-2) was 71.1° C. The in-lineintermediate branching catalyst formulation was formed in R2 byinjecting a solution of diethyl aluminum ethoxide into R2. The quantityof component (vii), i.e. ‘R2 (vii) (ppm)’ added to reactor 2 (R2) wasshown in Table 1a; to be more clear, in Example 1 the solution in R2contained 6.4 ppm of TiCl₄. The mole ratios of the in-line intermediatebranching catalyst components were also shown in Table 1a, specifically:(vi)/(v) or (tertiary butyl chloride)/(butyl ethyl magnesium);(viii)/(vii) or (diethyl aluminum ethoxide)/(titanium tetrachloride),and; (ix)/(vii) or (triethyl aluminum)/(titanium tetrachloride). InExample 1, the following mole ratios were used to synthesize the in-lineintermediate branching catalyst formulation: R2 (vi)/(v)=1.78; R2(viii)/(vii)=1.35, and; R2 (ix)/(vii)=0.35. Referring to FIG. 19 , inExamples 1 and 2, 100% of the diethyl aluminum ethoxide in stream 10 d,component (viii), was added to reactor 12 a via stream 10 h.

Average residence time of the solvent in a reactor is primarilyinfluenced by the amount of solvent flowing through each reactor and thetotal amount of solvent flowing through the solution process, in thecase of Examples 1 and 2 the typical average reactor residence times forR2 and R2 was about 73 and 50 seconds, respectively (R3 volume 18 L (4.8gallons)).

Polymerization in the continuous solution polymerization process wasterminated by adding a catalyst deactivator to the third exit streamexiting the tubular reactor (R3). The catalyst deactivator used wasoctanoic acid (caprylic acid), commercially available from P&GChemicals, Cincinnati, Ohio, U.S.A. The catalyst deactivator was addedsuch that the moles of fatty acid added were 50% of the total molaramount of titanium and aluminum added to the polymerization process;i.e. moles of octanoic acid added=0.5×(moles titanium+moles aluminum);this mole ratio was consistently used in all examples.

A two-stage devolitizing process was employed to recover the ethyleneinterpolymer product from the process solvent, i.e. two vapor/liquidseparators were used and the second bottom stream (from the second V/Lseparator) was passed through a gear pump/pelletizer combination. DHT-4V(hydrotalcite), supplied by Kyowa Chemical Industry Co. LTD, Tokyo,Japan was used as a passivator, or acid scavenger. A slurry of DHT-4V inprocess solvent was added prior to the first V/L separator. The molaramount of DHT-4V added was 10-fold higher than the molar amount oftertiary butyl chloride and titanium tetrachloride added to the solutionprocess.

Prior to pelletization the ethylene interpolymer product was stabilizedby adding about 500 ppm of Irganox 1076 (a primary antioxidant) andabout 500 ppm of Irgafos 168 (a secondary antioxidant), based on weightof the ethylene interpolymer product. Antioxidants were dissolved inprocess solvent and added between the first and second V/L separators.The targeted ethylene interpolymer product was 1.0 melt index (12) (ASTMD1239, 2.16 kg load, 190° C.) and 0.920 g/cm³ (ASTM D792). As shown inTable 1b, Examples 1 was produced at production rates of 98.3 kg/hr.

Batch Intermediate Branching Catalyst Formulation

Using a batch intermediate branching catalyst formulation anintermediately branched ethylene interpolymer product was prepared inthe pilot plant (described above); specifically, Example 4 in Tables 1aand 1b.

The batch intermediate branching procatalyst was injected into R2 usinga batch delivery system. The batch delivery system consisted of anagitated catalyst storage tank, recirculation loop, a metering pump andsolvent diluent loop. The batch intermediate branching procatalyst wasprepared in the Catalyst Synthesis Unit (CSU), described below, andtransferred to the agitated catalyst storage tank using nitrogen. Oncetransferred, the agitator in the catalyst storage tank and therecirculation pump were started to keep the batch intermediate branchingprocatalyst suspended to maintain a constant composition in the slurry.The temperature in the storage tank was maintained at ambienttemperature and the tank pressure was 300 kPag. The batch intermediatebranching procatalyst was transferred from the storage tank to thereactor using the metering pump and a high flow solvent diluent. To bemore clear, the discharge from the metering pump was combined with ahigh flow solvent diluent having a flow rate of 15 kg/hr; the diluentwas used to facilitate procatalyst injection into R2. A flow meterrecorded the flow rate of the combined batch intermediate branchingprocatalyst and the high flow diluent. The amount of batch intermediatebranching procatalyst injected into R2 was controlled/adjusted bychanging the metering pump's variable frequency drive or pump stroker.The co-catalyst, diethyl aluminum ethoxide (component (viii)), wasinjected into the reactor (R2) through a separate line forming theactive batch intermediate branching catalyst formulation. Typically,procatalyst flow rate was adjusted such that more than 80% of theethylene was converted to polyethylene in R2. The quantity of the batchintermediate branching catalyst formulation added to R2 was expressed asthe parts-per-million (ppm) of component (vii) in the reactor solution,i.e. R2 batch (vii) was 0.97 ppm for Example 4, as shown in Table 1a;the R2 batch (viii)/(vii) was 4.0, stream 60 e flow rate was 30,370 g/hrand the R2 batch catalyst inlet temperature was 31.9° C. The physicalproperties of Example 4 were summarized in Table 2.

Batch Intermediate Branching Procatalyst Formulation

The batch intermediate branching procatalyst was prepared in theCatalyst Synthesis Unit (CSU). The CSU included a continuously stirredtank reactor coded CSU-1, having a volume of 2.1 L, designed forpressures up to 20.6 MPa and temperatures up to 350° C. As describedbelow, the batch intermediate branching procatalyst was prepared in abatch-wise fashion in CSU-1 from the following components: component(v), butyl ethyl magnesium; component (vi), tertiary butyl chloride;component (vii), titanium tetrachloride; component (viii), diethylaluminum ethoxide, and; component (x), isobutyl aluminum dichloride.First, magnesium dichloride was formed in CSU-1. Although the MgCl₂reaction did not require pressure, CSU-1 was operated at 100 psi N₂pressure to ensure inert conditions, temperature was controlled at 50°C. using a recirculating heating bath connected to the jacket on CSU-1and agitator speed was 600 rpm. Using diaphragm pumps, components (v)and (vi) were continuously added to CSU-1 from their respective 5.5 Lreagent vessels such that the [component (vi)]/[component (v)] moleratio was about 2.2. After about 100 minutes 1.5 L of MgCl₂ slurry hadbeen collected in CSU-1 and the flows of components (v) and (vii) werestopped. Using a diaphragm pump component (x), stored in a 0.15 Lreagent vessel, was pumped to CSU-1 and the reactor was stirred at 50°C. for an additional 15 minutes; the [(component (x)]/[(component (v)]mole ratio was about 0.23. Using a diaphragm pump component (vii),stored in a 0.15 L reagent vessel, was pumped to CSU-1 and the reactorwas stirred at 50° C. for an additional 10 minutes; the [(component(v)]/[(component (vii)] mole ratio was about 7.5. The batch intermediatebranching procatalyst formulation was formed by adding component (viii).Using a diaphragm pump, component (viii) was pumped from its 0.15 Lreagent vessel to CSU-1 and the reactor was heated to 85° C. and stirredfor 90 minutes; the [(component (viii)]/[(component (vii)] mole ratiowas from about 1.0 to about 1.65. The batch intermediate branchingprocatalyst was pumped from CSU-1 to the catalyst storage tank andinjected in R2 was required.

Mixed Catalyst Examples

The following examples were presented to illustrate embodiments ofethylene interpolymer products produced using two catalyst formulations;these interpolymers contained a component A and a component B; whereincomponent B contained intermediate branching and component A did notcontain intermediate branching and may, or may not, contain long chainbranching. It is understood that the following examples do not limit theclaims presented.

The solution pilot plant described above was used to manufacture Example5. Tables 10a and 10b disclosed the process conditions employed tomanufacture Example 5; where an unbridged single site catalystformulation was employed in reactor 1 (R1) and an in-line intermediatebranching catalyst formulation (fully described above) was employed inreactor 2 (R2). The unbridged single site catalyst formulation includedthe following components: component (i), cyclopentadienyl tri(tertiarybutyl)phosphinimine titanium dichloride, (Cp[(t-Bu)₃PN]TiCl₂)(abbreviated PIC-1 in Table 10a); component (ii), methylaluminoxane(MAO-07); component (iii), trityl tetrakis(pentafluoro-phenyl)borate,and; component (iv), 2,6-di-tert-butyl-4-ethylphenol. The unbridgedsingle site catalyst component solvents used were methylpentane forcomponents (ii) and (iv) and xylene for components (i) and (iii). Thequantity of PIC-1 added “R1 (i) (ppm)” was 0.12 ppm; i.e. the solutionin R1 contained 0.12 ppm of PIC-1. The mole ratios of the catalystcomponents in R1 were: (ii)/(i) or [(MAO-07)/(PIC-1)] was 100; (iv)/(ii)or [(2,6-di-tert-butyl-4-ethylphenol)/(MAO-07)] was 0.0, and; (iii)/(i)or [(trityl tetrakis(pentafluoro-phenyl)borate)/(PIC-1)] was 1.1.Additional solution process parameters are disclosed in Table 10b; forexample, given the ethylene splits of 40/60 (ES^(R1)/ES^(R2)), Example 5contained about 40 wt % of component A and about 60 wt % of component B.PIC-1 produced an ethylene/1-octene interpolymer, component A, that didnot contain long chain branching or intermediate branching. The in-lineintermediate branching catalyst formulation produced anethylene/1-octene interpolymer, component B, that contained intermediatebranching and did not contain long chain branching. In Example 5, theaverage solution temperature during HUT-1, T^(HUT-1) was 64.0° C.; andthe average solution temperature during HUT-2 T^(HUT-2) was 70.5° C. Thein-line intermediate branching catalyst formulation was formed in R2 byinjecting a solution of diethyl aluminum ethoxide into R2.

The solution pilot plant described above was also used to manufactureExamples 10 and 11. Examples 10 and 11 were manufactured employing abridged metallocene catalyst formulation in reactor 1 (R1) and thein-line intermediate branching catalyst formulation (described above) inreactor 2 (R2) as shown in Tables 10a and 10b. The following componentswere used to prepare the bridged metallocene catalyst formulation:component (i),diphenylmethylene(cyclopentadienyl)(2,7-di-t-butylfuorenyl) hafniumdimethyl, [(2,7-tBu₂Flu)Ph₂C(Cp)HfMe₂] (abbreviated CpF-2 in Table 10a);component (ii) methylaluminoxane (MMAO-07); component (iii) trityltetrakis(pentafluoro-phenyl)borate, and; component (iv)2,6-di-tert-butyl-4-ethylphenol.

The bridged metallocene catalyst component solvents used weremethylpentane for components (ii) and (iv) and xylene for components (i)and (iii). The quantity of CpF-2 added “R1 (i) (ppm)” was 0.38 ppm; i.e.the solution in R1 contained 0.38 ppm of CpF-2. In the case of Example10, the mole ratios of the catalyst components in R1 were: (ii)/(i) or[(MAO-07)/(CpF-2)] was 64.2; (iv)/(ii) or[(2,6-di-tert-butyl-4-ethylphenol)/(MAO-07)] was 0.16, and; (iii)/(i) or[(trityl tetrakis(pentafluoro-phenyl)borate)/(CpF-2)] was 1.20.Additional solution process parameters were disclosed in Table 10b.Example 10 was manufactured with R1 and R2 operating in series mode andgiven an ethylene split of 50/50 (ES^(R1)/ES^(R2)); i.e. Example 10contained about 50 wt % of a component A and about 50 wt % of acomponent B. Example 11 was manufactured with R1 and R2 operating inparallel mode and given an ethylene split of 40/60 (ES^(R1)/ES^(R2))Example 11 contained about 40 wt % of a component A and about 60 wt % ofa component B. CpF-2 produced an ethylene/1-octene interpolymer,component A, that contained long chain branching but did not containintermediate branching. The in-line intermediate branching catalystformulation produced an ethylene/1-octene interpolymer, component B,that contained intermediate branching and did not contain long chainbranching. In Example 10, the average solution temperature during HUT-1,T^(HUT-1) was 65.3° C.; and the average solution temperature duringHUT-2, T^(HUT-2) was 62.8° C. In Example 11, the average solutiontemperature during HUT-1, T^(HUT-1) was 64.8° C.; and the averagesolution temperature during HUT-2, T^(HUT-2) was 66.1° C. In bothExamples 10 and 11, the in-line intermediate branching catalystformulation was formed in R2 by injecting a solution of diethyl aluminumethoxide into R2.

Blown Films

The following examples are presented for the purpose of illustratingembodiments of manufactured articles, specifically blown films; it beingunderstood that articles of manufacture are not limited to blown films.

Monolayer blown films were produced on a monolayer blown film line(Macro Engineering, Mississauga, Ontario, Canada). This line wasequipped with: a 3-inch diameter (7.62-cm) barrel; a Maddox mixingscrew; a low pressure, four-port spiral mandrel die with a 35 mil (0.089cm) die gap; and a dual ring. Blown films were produced at thicknessesof 1.0, 2.0 and 4.0 mil (25.4, 50.8 and 101.6 μm) employing theexperimental conditions disclosed in Table 22. Examples 2 and 3 wereproduced in the solution pilot plant (described above) using an in-lineintermediate branching catalyst formulation and similar processconditions as those used to manufacture Example 1 (0.9191 g/cm³, 0.90dg/min) as disclosed in Tables 1a and 1b; Example 2 was anethylene/1-octene interpolymer having a density of 0.9208 g/cm³ and amelt index of 1.02; Example 3 was an ethylene/1-octene interpolymerhaving a density of 0.9200 g/cm³ and a melt indexes of 0.96 dg/min.Given the fact that Examples 2 and 3 were manufactured using a similarin-line intermediate branching catalyst formulation, the same pilotplant and similar process conditions; Examples 2 and 3 contained a levelof intermediate branching similar to Example 1. Comparative 2 was anethylene/1-octene interpolymer produced with a comparative batchZiegler-Natta catalyst formulation that did not produce intermediatebranching; the physical properties of Comparative 2 were summarized inTable 2, e.g. 0.9208 g/cm³ and 0.97 dg/min.

Table 23 disclosed the blown film properties of: (i) Example 2; about 1mil film; (ii) Example 3, about 2 mil and about 4 mil films; and (iii)Comparative Example 2, about 2 mil and about 4 mil films. At least oneadvantage of films manufactured from ethylene interpolymer productshaving intermediate branching was an improved (higher) dart impact;relative to comparative films manufactured from comparative ethyleneinterpolymer products that do not contain intermediate branching. Morespecifically, as disclosed in Table 23, the 2 mil film prepared fromExample 3 had a dart impact of 365 g/mil which was 109% improvedrelative to the dart impact of the film prepared from Comparative 2,i.e. 175 g/mil. Similarly, the 4 mil film prepared from Example 3 had adart impact of 256 g/mil which was 71% improved relative to the dartimpact of the film prepared from Comparative 2, i.e. 150 g/mil.

Table 24 compares the monolayer blown film properties of Example 6 withComparative 9. Example 6 has been discussed previously. Example 6 was anethylene/1-octene interpolymer product containing the following twocomponents: A) about 40 wt % of a first ethylene interpolymer producedusing an unbridged single site catalyst formulation in a first reactor;and B) about 60 wt % of a second ethylene interpolymer produced using anin-line intermediate branching catalyst formulation in a second reactor;where the two reactors were operated in series. As shown in Table 24,Example 6 and Comparative 9 had the same density and melt index.However, Comparative 9 did not contain intermediate branching.Comparative 9 was an ethylene/1-octene interpolymer product containingtwo components: A) about 40 wt % of a first ethylene interpolymerproduced using an unbridged single site catalyst formulation in a firstreactor; and B) about 60 wt % of a second ethylene interpolymer producedusing an unbridged single site catalyst formulation in a second reactor(same catalyst in both reactors); where the two reactors were operatedin series. Several advantages of films manufactured from ethyleneinterpolymer products having intermediate branching are evident in Table24; relative to the Comparative 9 film. For example, monolayer films(1.0 mil) prepared from Example 6 had improved (higher) dart impactrelative to Comparative 9 monolayer films (1.0 mil); i.e. 824 g,relative to 475 g, respectively, a 74% higher dart impact. The Example 6film had improved (higher) machine direction (MD) tensile strengthrelative to the Comparative 9 film; i.e. 56 MPa, relative to 49 MPa,respectively, a 14% higher MD tensile strength. The Example 6 film hadimproved (higher) transverse direction (TD) tensile strength relative tothe Comparative 9 film; i.e. 47 MPa, relative to 40 MPa, respectively,an 18% higher TD tensile strength. Example 6 films also had improvedoptical properties relative to Comparative 9 films. Specifically, theExample 6 film had improved (higher) 45⁰ gloss relative to theComparative 9 film, i.e. 73, relative to 35, respectively, which was a108% improvement in film 450 gloss; and the film haze was improved(lower); i.e. 11%, relative to 22%, respectively, a −73% improvement infilm haze.

Testing Methods

Prior to testing, each specimen was conditioned for at least 24 hours at23±2° C. and 50±10% relative humidity and subsequent testing wasconducted at 23±2° C. and 50 +10% relative humidity. Herein, the term“ASTM conditions” refers to a laboratory that is maintained at 23±2° C.and 50±10% relative humidity; and specimens to be tested wereconditioned for at least 24 hours in this laboratory prior to testing.ASTM refers to the American Society for Testing and Materials.

Density

Ethylene interpolymer density was determined using ASTM D792-13 (Nov. 1,2013).

Melt Index

Ethylene interpolymer melt index was determined using ASTM D1238 (Aug.1, 2013). Melt indexes, I₂, I₆, I₁₀ and I₂₁ were measured at 190° C.,using weights of 2.16 kg, 6.48 kg, 10 kg and a 21.6 kg respectively. Theterms High Load Melt Index (HLMI) and I₂₁ are equivalent. The term MeltFlow Ratio (MFR) is defined as I₂₁/I₂. Herein, the term “stressexponent” or its acronym “S.Ex.”, is defined by the followingrelationship:

S.Ex.=log(I ₆ /I ₂)/log(6480/2160)

wherein I₆ and I₂ are the melt flow rates measured at 190° C. using 6.48kg and 2.16 kg loads, respectively.

Conventional Size Exclusion Chromatography (SEC)

Ethylene interpolymer (polymer) solutions (1 to 3 mg/mL) were preparedby heating the polymer in 1,2,4-trichlorobenzene (TCB) and rotating on awheel for 4 hours at 150° C. in an oven. An antioxidant(2,6-di-tert-butyl-4-methylphenol (BHT)) was added to the mixture inorder to stabilize the polymer against oxidative degradation. The BHTconcentration was 250 ppm. Polymer solutions were chromatographed at140° C. on a PL 220 high-temperature chromatography unit equipped withfour Shodex columns (HT803, HT804, HT805 and HT806) using TCB as themobile phase with a flow rate of 1.0 mL/minute, with a differentialrefractive index (DRI) as the concentration detector. BHT was added tothe mobile phase at a concentration of 250 ppm to protect GPC columnsfrom oxidative degradation. The sample injection volume was 200 μL. TheGPC columns were calibrated with narrow distribution polystyrenestandards. The polystyrene molecular weights were converted topolyethylene molecular weights using the Mark-Houwink equation, asdescribed in the ASTM standard test method D6474-12 (December 2012). TheGPC raw data were processed with the Cirrus GPC software, to producemolar mass averages (M_(n), M_(w), M_(z)) and molar mass distribution(e.g. Polydispersity, M_(w)/M_(n)). In the polyethylene art, a commonlyused term that is equivalent to SEC is GPC, i.e. Gel PermeationChromatography.

Triple Detection Size Exclusion Chromatography (3D-SEC)

Ethylene interpolymer (polymer) sample solutions (1 to 3 mg polymer/mL)were prepared by heating the polymer in 1,2,4-trichlorobenzene (TCB) androtating on a wheel for 4 hours at 150° C. in an oven. An antioxidant(2,6-di-tert-butyl-4-methylphenol (BHT)) was added to the mixture tostabilize the polymer against oxidative degradation. The BHTconcentration was 250 ppm. Sample solutions were chromatographed at 140°C. on a PL 220 high temperature chromatography unit equipped with adifferential refractive index (DRI) detector, a dual-angle lightscattering detector (15 and 90 degree) and a differential viscometer.The SEC columns used were either four Shodex columns (HT803, HT804,HT805 and HT806), or four PL Mixed ALS or BLS columns. TCB was themobile phase with a flow rate of 1.0 mL/minute, BHT was added to themobile phase at a concentration of 250 ppm to protect SEC columns fromoxidative degradation. The sample injection volume was 200 μL. The SECraw data were processed with the Cirrus GPC software, to produceabsolute molar masses and intrinsic viscosity ([71]) and viscosityaverage molar mass (M_(v)). The term “absolute” molar mass was used todistinguish 3D-SEC determined absolute molar masses from the molarmasses determined by conventional SEC. The viscosity average molar mass(M_(v)) and intrinsic viscosity ([71]) determined by 3D-SEC were used incalculations to determine the Long Chain Branching Factor (LCBF).

Triple Detection Cross Fractionation Chromatography (3D-CFC)

A polymer sample (150 to 300 mg) was introduced into the sampledissolution vessel of the Polymer Char Crystaf-TREF unit. The sampledissolution vessel was then filled with 35 ml 1,2,4-trichlorobenzene(TCB) containing 250 ppm antioxidant 2,6-di-tert-butyl-4-methylphenol(BHT), heated to the desired dissolution temperature (e.g. 140° C.) andstirred for 2 to 3 hours. The polymer solution (1.5 ml) was then loadedinto the TREF column filled with stainless steel beads. After beingallowed to equilibrate at a given stabilization temperature (e.g. 110°C.) for 20 to 45 minutes, the polymer solution was allowed tocrystallize with a temperature drop from the stabilization temperatureto 30° C. (0.2° C./minute). After equilibrating at 30° C. for 90minutes, the crystallized sample was eluted with TCB from 30 to 140° C.,while dividing the effluent into a number of fractions (e.g. 5 to 20fractions). For each fraction, the TREF column was heated (the heatingrate in the step-elution was 1.0° C./minute) to the specific dissolutiontemperature and maintained at that temperature for at least 50 minutebefore the solution of the fraction was eluted and introduced directlyto a SEC system through a heated transfer line. All above steps,including the sample dissolution, sample solution loading into TREFcolumn, crystallization and elution, were programmed and controlled withthe Polymer Char TREF software with the step-elution capability. Thevarious polymer fractions were chromatographed at 140° C. on a PL 220high-temperature chromatography unit equipped with either four Shodexcolumns (HT803, HT804, HT805 and HT806), or four PL Mixed ALS or BLScolumns, and with a differential refractive index (DRI) as theconcentration detector. A dual-angle light scattering detector (15 and90 degree) and a differential viscometer were used to measure the molarmass and intrinsic viscosity, respectively. TCB was the mobile phasewith a flow rate of 1.0 mL/minute, BHT was added to the mobile phase ata concentration of 250 ppm to protect SEC columns from oxidativedegradation. The data were acquired using Cirrus GPC software andprocessed with Cirrus GPC software and Excel spreadsheet to produceabsolute molar masses and intrinsic viscosity [71]. The term “absolute”molar mass was used to distinguish 3D-SEC determined absolute molarmasses from the molar masses determined by conventional SEC. Theviscosity average molar mass (M_(v)) and intrinsic viscosity [11] ofeach 3D-CFC TREF fraction determined by 3D-CFC were used in calculationsto determine the Non-Comonomer Index (NCI^(f)) and the Non-ComonomerIndex Distribution (NCID_(i)).

Referring to Eq. (4) where NCI^(f) was defined; (M_(v) ^(f)) (g/mole)and [η]^(f) (dL/g) were the viscosity average molar mass and theintrinsic viscosity, respectively, of the f^(th) TREF fraction asdetermined with 3D-CFC; T^(f) was the weight average TREF elutiontemperature of the f^(fh) TREF fraction (details regarding T^(f) aredescribed below); and A, B and C were constants specific to the α-olefincomonomer in the ethylene/α-olefin interpolymer under test. In the caseof 1-octene: A was 2.1626; B was −0.6737 and C was 63.6727. Constants A,B and C for other α-olefins were determined experimentally (non-limitingexamples include 1-hexene). Elaborating, a series of linearethylene/α-olefin interpolymers with different comonomer contents wereanalyzed with triple detection size exclusion chromatography (3D-SEC) inTCB at 140° C., in which the viscosity average molar masses (M_(v)) andthe intrinsic viscosities ([η]) of the linear ethylene/α-olefininterpolymers were determined and were used to calculate theMark-Houwink constants K based on the Mark-Houwink equation([η]=K×(M_(v))^(α)). Well-known to those of ordinary experience, theMark-Houwink constant α is 0.725 for ethylene/α-olefin interpolymers.Using simple regression, a plot of Mark-Houwink constants K versuscomonomer contents [CH₃/1000C] of the linear ethylene/α-olefininterpolymers generated the following relationship:

K=(slope)[CH3/1000C]+intercept  Eq.(16)

In this disclosure, the constant A in Eq. (4) was defined by the (slope)in Eq. (16); specifically, A=−1000000×(slope). The constants B and C inEq. (4) were calculated from the linear correlation between comonomercontents and the weight average elution temperatures ofethylene/α-olefin interpolymers based on re-constructed analytical TREFprofiles of the ethylene/α-olefin interpolymers (see details below); theconstant B was the slope and the constant C was the intercept. Forexample, in this disclosure for α-octene comonomer, constants A, B and Cwere 2.1626, −0.6737 and 63.6727 respectively.

T^(f), in Eq. (4), the weight average TREF elution temperature of thef^(th) 3D-CFC TREF fraction, was calculated based on the re-constructedanalytical TREF profile of the ethylene/α-olefin interpolymer. There-constructed analytical TREF profile was obtained by simply replacingthe original elution temperatures in analytical TREF analysis performedon a Polymer Char Crystaf-TREF instrument, hereafter CTREF, with theequivalents of 3D-CFC elution temperature. The conversion of theoriginal elution temperatures to the equivalents of 3D-CFC elutiontemperature enables one to compensate for differences in flow during theelution stage, i.e. dynamic (with a flow) while heating in CTREF, incontrast with static elution (without a flow) while heating in 3D-CFC;as well as for any other difference between these instruments (if any).To do this conversion, a series of ethylene/α-olefin interpolymershaving different comonomer contents and randomly distributed comonomerunits were analyzed with both CTREF (Polymer Char Crystaf-TREF unit) and3D-CFC. In this calibration procedure, the range of elution temperaturein 3D-CFC analysis for each TREF fraction was very narrow (e.g., 1 to 2degrees whenever possible and not greater than 5 degrees) and theaverage of the low and high temperatures of the TREF fraction was usedto define the elution temperature of the 3D-CFC TREF fraction, e.g.42.5° C. was the elution temperature for the 40° C. to 45° C. fraction.The weight average elution temperature of the entire ethylene/α-olefininterpolymer was calculated from the weight fraction and the elutiontemperature of each 3D-CFC TREF fraction. From the correlations betweencomonomer contents and the weight average elution temperatures ofethylene/α-olefin interpolymers in 3D-CFC and CTREF, the relationbetween the weight average elution temperatures between 3D-CFC and CTREFcould be established and this relation was used to convert the originalelution temperatures in CTREF analysis to 3D-CFC elution temperatures.In this disclosure, the relation between the weight average elutiontemperatures of 3D-CFC (T_(CFC)) and the weight average elutiontemperatures of CTREF (T_(CTREF)) was described by the followingrelationship.

T _(CFC)=0.9776 T _(CTREF)−0.7156

This relationship was used to convert the original CTREF elutiontemperatures to the equivalents of 3D-CFC elution temperature inre-construction of the analytical TREF profiles, for calculating theT^(f), the weight average TREF elution temperature of the f^(th) 3D-CFCTREF fraction and for calculating the constants B and C in Eq. (4).

Dynamic Mechanical Analysis (DMA)

Oscillatory shear measurements under small strain amplitudes werecarried out to obtain linear viscoelastic functions at 190° C. undernitrogen atmosphere, at a strain amplitude of 10% and over a frequencyrange of 0.02-126 rad/s at 5 points per decade. Frequency sweepexperiments were performed with a TA Instruments DHR3 stress-controlledrheometer using cone-plate geometry with a cone angle of 5°, atruncation of 137 μm and a diameter of 25 mm. In this experiment asinusoidal strain wave was applied and the stress response was analyzedin terms of linear viscoelastic functions. The zero shear rate viscosity(η₀) based on the DMA frequency sweep results was determined using theEllis model (see R. B. Bird et al. “Dynamics of Polymer Liquids. Volume1: Fluid Mechanics” Wiley-Interscience Publications (1987) p. 228).

Composition Distribution Branching Index (CDBI)

The “Composition Distribution Branching Index”, hereinafter CDBI, of thedisclosed Examples and Comparative Examples were measured using aCRYSTAF/TREF 200+unit equipped with an IR detector, hereinafter CTREF.The acronym “TREF” refers to Temperature Rising Elution Fractionation.The CTREF was supplied by PolymerChAR S.A. (Valencia Technology Park,Gustave Eiffel, 8, Paterna, E-46980 Valencia, Spain). The CTREF wasoperated in the TREF mode, which generates the chemical composition ofthe polymer sample as a function of elution temperature, the Co/Ho ratio(Copolymer/Homopolymer ratio) and the CDBI (the Composition DistributionBreadth Index), i.e. CDBI₅₀. A polymer sample (80 to 100 mg) was placedinto the reactor vessel of the CTREF. The reactor vessel was filled with35 ml of 1,2,4-trichlorobenzene (TCB) and the polymer was dissolved byheating the solution to 150° C. for 2 hours. An aliquot (1.5 mL) of thesolution was then loaded into the CTREF column which was packed withstainless steel beads. The column, loaded with sample, was allowed tostabilize at 110° C. for 45 minutes. The polymer was then crystallizedfrom solution, within the column, by dropping the temperature to 30° C.at a cooling rate of 0.09° C./minute. The column was then equilibratedfor 30 minutes at 30° C. The crystallized polymer was then eluted fromthe column with TCB flowing through the column at 0.75 mL/minute, whilethe column was slowly heated from 30° C. to 120° C. at a heating rate of0.25° C./minute. The raw CTREF data were processed using Polymer ChARsoftware, an Excel spreadsheet and CTREF software developed in-house.CDBI₅₀ was defined as the percent of polymer whose composition waswithin 50% of the median comonomer composition; CDBI₅₀ was calculatedfrom the composition distribution cure and the normalized cumulativeintegral of the composition distribution curve, as described in U.S.Pat. No. 5,376,439. Those skilled in the art will understand that acalibration curve was required to convert a CTREF elution temperature tocomonomer content, i.e. the amount of comonomer in the ethylene/α-olefinpolymer fraction that eluted at a specific temperature. The generationof such calibration curves were described in the prior art, e.g. Wild,et al., J. Polym. Sci., Part B, Polym. Phys., Vol. 20 (3), pages441-455: hereby fully incorporated by reference. At the end of eachsample run, the CTREF column was cleaned for 30 minutes; specifically,with the CTREF column temperature at 160° C., TCB flowed (0.5 mL/minute)through the column for 30 minutes.

Neutron Activation (Elemental Analysis)

Neutron Activation Analysis, hereinafter N.A.A., was used to determinecatalyst residues in ethylene interpolymer products as follows. Aradiation vial (composed of ultrapure polyethylene, 7 mL internalvolume) was filled with an ethylene interpolymer product sample and thesample weight was recorded. Using a pneumatic transfer system the samplewas placed inside a SLOWPOKE™ nuclear reactor (Atomic Energy of CanadaLimited, Ottawa, Ontario, Canada) and irradiated for 30 to 600 secondsfor short half-life elements (e.g., Ti, V, Al, Mg, and Cl) or 3 to 5hours for long half-life elements (e.g. Zr, Hf, Cr, Fe and Ni). Theaverage thermal neutron flux within the reactor was 5×10¹¹/cm²/s. Afterirradiation, samples were withdrawn from the reactor and aged, allowingthe radioactivity to decay; short half-life elements were aged for 300seconds or long half-life elements were aged for several days. Afteraging, the gamma-ray spectrum of the sample was recorded using agermanium semiconductor gamma-ray detector (Ortec model GEM55185,Advanced Measurement Technology Inc., Oak Ridge, Tenn., USA) and amultichannel analyzer (Ortec model DSPEC Pro). The amount of eachelement in the sample was calculated from the gamma-ray spectrum andrecorded in parts per million relative to the total weight of theethylene interpolymer product sample. The N.A.A. system was calibratedwith Specpure standards (1000 ppm solutions of the desired element(greater than 99% pure)). One mL of solutions (elements of interest)were pipetted onto a 15 mm×800 mm rectangular paper filter and airdried. The filter paper was then placed in a 1.4 mL polyethyleneirradiation vial and analyzed by the N.A.A. system. Standards are usedto determine the sensitivity of the N.A.A. procedure (in counts/μg).

Unsaturation

The quantity of unsaturated (Unsat.) groups, i.e. double bonds, in anethylene interpolymer product was determined according to ASTM D3124-98(vinylidene unsaturation, published March 2011) and ASTM D6248-98 (vinyland trans unsaturation, published July 2012). An ethylene interpolymerproduct sample was: a) first subjected to a carbon disulfide extractionto remove additives that may interfere with the analysis; b) the sample(pellet, film or granular form) was pressed into a plaque of uniformthickness (0.5 mm), and; c) the plaque was analyzed by FTIR.

Comonomer Content: Fourier Transform Infrared (FTIR) Spectroscopy

The quantity (mol % (or wt %)) of comonomer in an ethylene interpolymerproduct was determined by FTIR and reported as the Short Chain Branching(SCB) content having dimensions of CH₃#/1000C (number of methyl branchesper 1000 carbon atoms). This test was completed according to ASTMD6645-01 (2001), employing a compression molded polymer plaque and aThermo-Nicolet 750 Magna-IR Spectrophotometer. The polymer plaque wasprepared using a compression molding device (Wabash-Genesis Seriespress) according to ASTM D4703-16 (April 2016).

Creep Test

Creep measurements were performed by an Anton Paar MCR 501 rheometer at190° C. using 25 mm parallel plate geometry under nitrogen atmosphere.In this experiment, a compression molded circular plaque with athickness of 1.8 mm was placed between the pre-heated upper and lowermeasurement fixtures and allowed to come to thermal equilibrium. Theupper plate was then lowered to 50 μm above the testing gap size of 1.5mm. At this point, the excess material was trimmed off and the upperfixture was lowered to the measurement gap size. A waiting time of 10min after sample loading and trimming was applied to avoid residualstresses causing the strain to drift. In the creep experiment, the shearstress was increased instantly from 0 to 20 Pa and the strain wasrecorded versus time. The sample continued to deform under the constantshear stress and eventually reached a steady rate of straining. Creepdata was reported in terms of creep compliance (J(t)) which has theunits of reciprocal modulus. The inverse of J(t) slope in the steadycreeping regime was used to calculate the zero shear rate viscositybased on the linear regression of the data points in the last 10% timewindow of the creep experiment.

In order to determine if the sample was degraded during the creep test,frequency sweep experiments under small strain amplitude (10%) wereperformed before and after creep stage over a frequency range of 0.1-100rad/s. The difference between the magnitude of complex viscosity at 0.1rad/s before and after the creep stage was used as an indicator ofthermal degradation. The difference should be less than 5% to considerthe creep determined zero shear rate viscosity acceptable.

Creep experiments confirmed that Linear Reference Line (see FIG. 18 )for linear ethylene interpolymers was also valid if the creep determinedη₀ was used rather than the DMA determined η₀. In this disclosure, theLCBF (Long Chain Branching Factor) was determined using the DMAdetermined η₀. To be absolutely clear, the zero shear viscosity (ZSV[poise]) data reported in Tables 19a, 19b, 20 and 21 were measured usingDMA.

Hexane Extractables (Plaque)

Hexane extractables using compression molded plaques were determinedaccording to ASTM D5227.

Film Dart Impact

Film dart impact strength was determined using ASTM D1709-09 Method A(May 1, 2009). In this disclosure the dart impact test employed a 1.5inch (38 mm) diameter hemispherical headed dart.

Film Tensile

The following film tensile properties were determined using ASTM D882-12(Aug. 1, 2012): tensile break strength (MPa), elongation at break (%),tensile yield strength (MPa), tensile elongation at yield (%) andtensile energy to break (J). Tensile properties were measured in theboth the machine direction (MD) and the transverse direction (TD) of theblown films.

Film Secant Modulus

The secant modulus is a measure of film stiffness. The secant modulus isthe slope of a line drawn between two points on the stress-strain curve,i.e. the secant line. The first point on the stress-strain curve is theorigin, i.e. the point that corresponds to the origin (the point of zeropercent strain and zero stress), and; the second point on thestress-strain curve is the point that corresponds to a strain of 1%;given these two points the 1% secant modulus is calculated and isexpressed in terms of force per unit area (MPa). The 2% secant modulusis calculated similarly. This method is used to calculated film modulusbecause the stress-strain relationship of polyethylene does not followHook's law; i.e. the stress-strain behavior of polyethylene isnon-linear due to its viscoelastic nature. Secant moduli were measuredusing a conventional Instron tensile tester equipped with a 200 lbf loadcell. Strips of monolayer film samples were cut for testing withfollowing dimensions: 14 inch long, 1 inch wide and 1 mil thick;ensuring that there were no nicks or cuts on the edges of the samples.Film samples were cut in both the machine direction (MD) and thetransverse direction (TD) and tested. ASTM conditions were used tocondition the samples. The thickness of each film was accuratelymeasured with a hand-held micrometer and entered along with the samplename into the Instron software. Samples were loaded in the Instron witha grip separation of 10 inch and pulled at a rate of 1 inch/mingenerating the strain-strain curve. The 1% and 2% secant modulus werecalculated using the Instron software.

Film Elmendorf Tear

Film tear performance was determined by ASTM D1922-09 (May 1, 2009); anequivalent term for tear is “Elmendorf tear”. Film tear was measured inboth the machine direction (MD) and the transverse direction (TD) of theblown films.

Film Opticals

Film optical properties were measured as follows: Haze, ASTM D1003-13(Nov. 15, 2013), and; Gloss ASTM D2457-13 (Apr. 1, 2013).

Film Hot Tack

In this disclosure, the “Hot Tack Test” was performed as follows, usingASTM conditions. Hot tack data was generated using a J&B Hot Tack Testerwhich is commercially available from Jbi Hot Tack, Geloeslaan 30, B-3630Maamechelen, Belgium. In the hot tack test, the strength of a polyolefinto polyolefin seal is measured immediately after heat sealing two filmsamples together (the two film samples were cut from the same roll of2.0 mil (51-μm) thick film), i.e. when the polyolefin macromoleculesthat comprise the film are in a semi-molten state. This test simulatesthe heat sealing of polyethylene films on high speed automatic packagingmachines, e.g., vertical or horizontal form, fill and seal equipment.The following parameters were used in the J&B Hot Tack Test: filmspecimen width, 1 inch (25.4 mm); film sealing time, 0.5 second; filmsealing pressure, 0.27 N/mm²; delay time, 0.5 second; film peel speed,7.9 in/second (200 mm/second); testing temperature range, 203° F. to293° F. (95° C. to 145° C.); temperature increments, 9° F. (5° C.); andfive film samples were tested at each temperature increment to calculateaverage values at each temperature. The following data was recorded forthe disclosed Example films and Comparative Example films: the “TackOnset @ 1.0 N (° C.)”, the temperature at which a hot tack force of 1Nwas observed (average of 5-film samples); “Hot tack Strength (N)” wasthe maximum hot tack force observed (average of 5-film samples) over thetesting temperature range.

Film Heat Seal Strength

In this disclosure, the “Heat Seal Strength Test” was performed asfollows. ASTM conditions were employed. Heat seal data was generatedusing a conventional Instron Tensile Tester. In this test, two filmsamples are sealed over a range of temperatures (the two film sampleswere cut from the same roll of 2.0 mil (51-μm) thick film). Thefollowing parameters were used in the Heat Seal Strength Test: filmspecimen width, 1 inch (25.4 mm); film sealing time, 0.5 second; filmsealing pressure, 40 psi (0.28 N/mm²); temperature range, 212° F. to302° F. (100° C. to 150° C.) and temperature increment, 9° F. (5° C.).After aging for at least 24 hours at ASTM conditions, seal strength wasdetermined using the following tensile parameters: pull (crosshead)speed, 12 inch/min (2.54 cm/min); direction of pull, 90° to seal, and; 5samples of film were tested at each temperature increment. The SealInitiation Temperature, hereinafter S.I.T., is defined as thetemperature required to form a commercially viable seal; a commerciallyviable seal has a seal strength of 2.0 lb per inch of seal (8.8 N per25.4 mm of seal).

Film Hexane Extractables

Hexane extractables was determined according to the Code of FederalRegistration 21 CFR § 177.1520 Para (c) 3.1 and 3.2; wherein thequantity of hexane extractable material in a film is determinedgravimetrically. Elaborating, 2.5 grams of 3.5 mil (89 μm) monolayerfilm was placed in a stainless steel basket, the film and basket wereweighed (w^(i)), while in the basket the film was: extracted withn-hexane at 49.5° C. for two hours; dried at 80° C. in a vacuum oven for2 hours; cooled in a desiccator for 30 minutes, and; weighed (w^(f)).The percent loss in weight is the percent hexane extractables (w^(C6)):w^(C6)=100×(w^(i)−w^(f))/w^(i).

TABLE la Continuous solution polymerization process parameters employingan intermediate branching catalyst formulation: Examples 1 and 4. SampleCode Example 1 Example 4 Intermediate Branching Catalyst In-line BatchR2 (vii) (ppm) 6.4 — R2 (vi)/(v) (mol ratio) 1.78 — R2 (viii)/(vii) (molratio) 1.35 — R2 (ix)/(vii) (mol ratio) 0.35 — component (vii), stream10c (g/h) 439.8 — component (viii), stream 10h (g/h) 140.6 — component(vi), stream 10b (g/h) 430.0 — components ((v) + (ix))¹, stream 10a463.4 — (g/h) solvent stream 10a′ (g/h) 3000 — solvent stream 10b′ (g/h)3000 — solvent stream 10c′ (g/h) 4900 — solvent stream 10f′ (g/h) 37600— R2 batch (vii) ppm — 0.97 R2 batch (viii)/(vii) (mol ratio) — 4.0 R2stream 60e (g/h) — 30370 R2 batch catalyst, Ti flow (g/h) Stream 60e′(g/h) — 30000 ¹Molar ratio of [component (ix)]/[component (v)] was 20/1

TABLE 1b Additional solution process parameters for Examples 1 and 4.Sample Code Example 1 Example 4 R2 total solution rate (kg/hr) 522.2427.3 Total Soluton Rate (kg/hr) 600.0 500.1 R2 ethylene concentration(wt %) 12.1 13.1 R3 ethylene concentration (wt %) 13.9 15.0 ES^(R2) (%)80.0 80.0 ES^(R3) 20.0 20.0 (1-octene/ethylene) total (wt.fr.) 0.50 0.46CS^(R2) (%) 100 100 CS^(R3) (%) 0.0 0.0 R2 Catalyst Inlet Temperature (°C.) 40.0 31.9 R2 inlet temp (° C.) 30.0 30.0 R2 Mean Temp (° C.) 183.1194.3 H₂ ^(R2) (ppm) 1.0 1.0 R3 volume (L) 18 18 R3 inlet temp (° C.)129.9 129.9 R3 exit temp (° C.) 211.9 221.0 H₂ ^(R3) (ppm) 0.50 0.5 R3ΔTemp (° C.) 28.8 26.7 Q^(T) (%) 90.0 93.2 Production Rate (kg/hr) 98.388.0

TABLE 2 Physical and molecular characteristics of Examples 1, 2 and 4;relative to Comparatives 1 and 2. Resin Code Example 1 Example 2 Example4 Comp. 1 Comp. 2 Comonomer 1-octene 1-octene 1-octene 1-octene 1-octeneDensity (g/cm³) 0.9191 0.9208 0.9186 0.9182 0.9208 I₂ (dg/min) 0.90 1.020.94 0.98 0.97 S.Ex. 1.32 1.32 1.31 1.31 1.30 MFR 29.0 30.9 29.1 28.229.5 M_(n) (g/mol) 29615 27100 35870 26682 33800 M_(w) (g/mol) 108052101100 116340 94018 121500 M_(z) (g/mol) 312107 302700 329736 245077329400 M_(w)/M_(n) 3.65 3.73 3.24 3.52 3.59 M_(z)/M_(w) 2.89 2.99 2.832.61 2.71 CDBI₅₀ (%) 51.4 n/a 53.0 54.0 n/a FTIR CoMo (mol %) 2.7 2.82.7 2.6 2.7 FTIR Branch Freq (CH₃/1000 C.) 13.5 14.2 13.7 13.2 13.7Unsat. Internal/100 C. 0.005 n/a n/a 0.004 n/a Unsat. Side Chain/100 C.0.011 n/a n/a 0.005 n/a Unsat. Terminal/100 C. 0.050 n/a n/a 0.039 n/aHexane Extractables, Plaque (%) 0.58 n/a 0.51 0.65 n/a Ti (ppm), N.A.A.7.52 n/a 12.84 1.7 Al (ppm), N.A.A. 94.5 n/a 186 8.8 Mg (ppm), N.A.A.348 n/a 387 12.0 Cl (ppm), N.A.A. 93.7 n/a 166 39.0

TABLE 3 3D-CFC characterization of Example 1 and Non-Comonomer Index.Elution SCB^(f) 3D-CFC Temp M_(w) × 10⁻⁵ M_(v) × 10⁻⁵ Avg. [n] (CH₃/1000Fraction (° C.) (wt.fr.)^(f) (g/mol) (g/mol) (dL/g) T^(f) (° C.) NCI^(f)C) F1 30-60 0.1699 0.723 0.637 0.98 51.42 0.983 29.03 F2 60-65 0.08210.93 0.837 1.26 62.64 0.980 21.47 F3 65-70 0.1131 1.05 0.962 1.42 67.630.981 18.11 F4 70-74 0.1059 1.09 0.996 1.49 72.05 0.983 15.13 F5 74-780.1201 1.14 1.04 1.56 76.01 0.981 12.46 F6 78-82 0.1203 1.27 1.14 1.6679.99 0.960  9.78 F7 82-87 0.1052 1.55 1.36 1.82 84.25 0.916  6.91 F887-92 0.0720 1.90 1.66 2.13 89.76 0.902  3.20 F9 92-110 0.1114 2.02 1.792.33 93.44 0.924  0.72

TABLE 4 3D-CFC characterization of Example 4 and Non-Comonomer Index.Elution SCB^(f) 3D-CFC Temp M_(w) × 10⁻⁵ M_(v) × 10⁻⁵ Avg. [n] (CH₃/1000Fraction (° C.) (wt.fr.)^(f) (g/mol) (g/mol) (dL/g) T^(f) (° C.) NCI^(f)C) F1 30-60 0.1666 0.616 0.544 0.88 50.84 0.985 29.42 F2 60-65 0.08310.869 0.786 1.21 62.63 0.980 21.48 F3 65-70 0.1166 0.969 0.888 1.3467.61 0.979 18.12 F4 70-74 0.1101 1.08 0.989 1.47 72.04 0.978 15.14 F574-78 0.1240 1.13 1.04 1.56 76.03 0.984 12.45 F6 78-82 0.1204 1.22 1.111.65 79.98 0.976  9.79 F7 82-88 0.1033 1.41 1.28 1.81 84.56 0.952  6.70F8 88-92 0.0456 1.70 1.54 2.10 90.06 0.938  3.00 F9 92-110 0.1304 2.061.89 2.49 94.45 0.951  0.04

TABLE 5 3D-CFC characterization of Comparative 1 and Non-ComonomerIndex. Elution SCB^(f) 3D-CFC Temp M_(w) × 10⁻⁵ M_(v) × 10⁻⁵ Avg. [n](CH₃/1000 Fraction (° C.) (wt.fr.)^(f) (g/mol) (g/mol) (dL/g) T^(f) (°C.) NCI^(f) C) F1 30-65 0.1921 0.604 0.517 0.87 54.98 1.00 26.63 F265-70 0.0928 0.878 0.785 1.25 67.67 1.00 18.08 F3 70-74 0.1094 1.050.954 1.46 72.11 0.994 15.09 F4 74-78 0.1511 1.15 1.06 1.61 76.09 1.0012.41 F5 78-82 0.1631 1.23 1.14 1.72 79.96 1.00  9.8 F6 82-88 0.12661.40 1.28 1.90 84.39 1.00  6.82 F7 88-92 0.0549 1.71 1.55 2.23 90.200.989  2.9 F8 92-110 0.1100 1.95 1.78 2.50 93.75 1.00  0.51

TABLE 6 3D-CFC characterization of Comparative 3 and Non-ComonomerIndex. Elution SCB^(f) 3D-CFC Temp M_(w) × 10⁻⁵ M_(v) × 10⁻⁵ Avg. [n](CH₃/1000 Fraction (° C.) (wt.fr.)^(f) (g/mol) (g/mol) (dL/g) T^(f) (°C.) NCI^(f) C) F1 30-65 0.1527 0.238 0.222 0.48 57.43 0.998 24.98 F265-70 0.1059 0.514 0.480 0.87 67.73 0.997 18.04 F3 70-73 0.1133 0.8840.817 1.30 71.64 0.995 15.41 F4 73-75 0.1408 1.31 1.23 1.77 74.09 1.00013.76 F5 75-76 0.0783 1.53 1.44 2.00 75.51 0.996 12.80 F6 76-77 0.11691.54 1.47 2.03 76.50 0.997 12.13 F7 77-78 0.0977 1.35 1.27 1.84 77.480.993 11.47 F8 78-85 0.1432 1.09 1.01 1.57 79.49 0.996 10.12 F9 85-1400.0512 2.15 2.04 2.75 92.16 0.995  1.58

TABLE 7 Physical and molecular characteristics of Comparatives 3, 4 and5. Resin Code Comparative 3 Comparative 4 Comparative 5 Comonomer1-octene 1-octene 1-octene Density (g/cm³) 0.9162 0.9018 0.9028 I₂(dg/min) 0.99 1.06 0.91 S.Ex. 1.27 1.41 1.44 MFR 30.8 29.5 31.1 M_(n)(g/mol) 33358 40133 45124 M_(w) (g/mol) 102603 83226 84299 M_(z) (g/mol)238331 148667 137468 M_(w)/M_(n) 3.08 2.07 1.87 M_(z)/M_(w) 2.32 1.791.93 CDBI₅₀ (%) 77.5 89.5 92.5 FTIR CoMo (mol %) 2.9 4.6 4.5 FTIR BranchFreq (CH₃/1000 C.) 14.6 23.2 22.3 Unsaturation Internal/100 C. 0.0210.006 0.014 Unsaturation Side Chain/100 C. 0.002 0.001 0.009Unsaturation Terminal/100 C. 0.006 0.008 0.009 Hexane Extractables,Plaque (%) 0.48 0.58 n/a Ti (ppm), N.A.A. 0.30 0.30 n/a Al (ppm), N.A.A.9.1 1.9 n/a Mg (ppm), N.A.A. n/d 2.0 n/a Cl (ppm), N.A.A. 0.47 0.9 n/aHf (ppm), N.A.A. n/a n/a 2.2

TABLE 8 3D-CFC characterization of Comparative 4 and Non-ComonomerIndex. Elution SCB^(f) 3D-CFC Temp M_(w) × 10⁻⁵ M_(v) × 10⁻⁵ Avg. [n](CH₃/1000 Fraction (° C.) (wt.fr.)^(f) (g/mol) (g/mol) (dL/g) T^(f) (°C.) NCI^(f) C) F1 30-50 0.1123 0.459 0.439 0.70 44.18 0.944 33.91 F250-55 0.1024 0.675 0.654 0.97 52.76 0.948 28.13 F3 55-58 0.0896 0.8270.804 1.15 56.60 0.943 25.54 F4 58-60 0.0726 0.87 0.850 1.21 59.05 0.94523.89 F5 60-62 0.108 0.978 0.956 1.32 61.04 0.942 22.55 F6 62-64 0.13861.080 1.05 1.44 63.03 0.947 21.21 F7 64-66 0.1435 1.110 1.09 1.49 64.990.948 19.89 F8 66-68 0.1111 1.100 1.08 1.47 66.93 0.94 18.58 F9 68-1100.1218 1.120 1.07 1.50 69.99 0.944 16.52

TABLE 9 3D-CFC characterization of Comparative 5 and Non-ComonomerIndex. Elution 3D-CFC Temp M_(w) × 10⁻⁵ M_(v) × 10⁻⁵ Avg. [n] SCB^(f)Fraction (° C.) (wt.fr.)^(f) (g/mol) (g/mol) (dL/g) T^(f) (° C.) NCI^(f)(CH₃/1000C) F1 30-55 0.1153 0.377 0.359 0.64 48.57 0.976 30.95 F2 55-600.1609 0.742 0.721 1.10 57.86 0.976 24.69 F3 60-63 0.1725 0.964 0.9411.35 61.62 0.973 22.16 F4 63-65 0.1650 1.12 1.10 1.53 64.05 0.974 20.52F5 65-67 0.2053 1.11 1.090 1.54 65.98 0.979 19.22 F6 67-110 0.1810 0.8950.866 1.31 68.70 0.973 17.39

TABLE 10a Mixed catalyst Continuous solution polymerization processparameters employing an intermediate branching catalyst formulation anda homogeneous catalyst formulation: Examples 5, 10 and 11. Sample CodeExample 5 Example 10 Example 11 Reactor Mode Series Series Parallel R1Catalyst (homogeneous) PIC-1 CpF-2 CpF-2 R2 Catalyst (intermediatebranching) In-line In-line In-line R1 (i) (ppm) 0.12 0.380 0.380 R1(ii)/(i) mole ratio 100 64.2 48 R1 (iv)/(ii) mole ratio 0 0.16 0.15 R1(iii)/(i) mole ratio 1.1 1.20 1.36 R2 (vii) (ppm) 4.2 5.16 7.24 R2(vi)/(v) (mol ratio) 2.07 2.07 2.07 R2 (viii)/(vii) (mol ratio) 1.351.35 1.35 R2 (ix)/(vii) (mol ratio) 0.35 0.35 0.35 component (vii),stream 10c (g/h) 326.9 354.0 179.2 component (viii), stream 10h (g/h)89.7 104.4 52.6 component (vi), stream 10b (g/h) 388.8 417.4 211.1components ((v) + (ix))¹, stream 10a (g/h) 391.8 389.4 201.6 solventstream 10a′ (g/h) 3200 2900 2470 solvent stream 10b′ (g/h) 3300 310029900 solvent stream 10c′ (g/h) 4700 4900 4900 solvent stream 10f′ (g/h)38600 37700 37600 ¹R1 catalyst component (i) was PIC-1 or CpF-2

TABLE 10b Additional solution process parameters for Examples 5, 10 and11. Sample Code Example 5 Example 10 Example 11 R1 total solution rate(kg/h) 358.8 387.3 352.0 R2 total solution rate (kg/hr) 241.2 162.7198.0 Total Solution Rate (kg/hr) 600 550 550 R1 ethylene concentration(wt %) 10.3 9.8 11.1 R2 ethylene concentration (wt %) 15.4 13.8 13.2 R3ethylene concentration (wt %) 15.4 13.8 13.2 ES^(R1) (%) 40 50.0 60.0ES^(R2) (%) 60 50.0 40.0 ES^(R3) 0 0.0 0.0 (1-octene/ethylene) total(wt.fr.) 0.67 0.31 0.29 CS^(R1) (%) 100 67 100 CS^(R2) (%) 0 33 0.0CS^(R3) (%) 0 0 0 R1 Catalyst Inlet Temperature (° C.) 32.5 30.6 31.4 R1Inlet Temperature (° C.) 30.0 30.0 30.0 R1 Mean Temperature (° C.) 141141.1 154.7 H₂ ^(R1) (ppm) 0.2 5.35 6.82 R2 Catalyst Inlet Temperature(° C.) 38.6 37.9 37.8 R2 inlet temp (° C.) 30 50 50 R2 Mean Temp (° C.)206 197.7 205.7 H₂ ^(R2) (ppm) 3.5 18 2.78 R3 volume (L) 18 2.2 2.2 R3inlet temp (° C.) 130.0 130 130 R3 exit temp (° C.) 214.0 197.7 181.6 H₂^(R3) (ppm) 0.0 0 0 Q^(T) (%) 93.1 90.8 89.9 Production Rate (kg/hr)94.8 72.0 61.5

TABLE 11 Physical and molecular characteristics of Examples 5-7 andComparative 6. Resin Code Example 5 Example 6 Example 7 Comp. 6Comonomer 1-octene 1-octene 1-octene 1-octene Density (g/cm³) 0.91600.9124 0.9210 0.9189 I₂ (dg/min) 1.00 0.92 0.85 0.89 S.Ex. 1.26 1.251.23 1.36 MFR 27.2 23.4 22.1 30.4 M_(n) (g/mol) 28655 42765 39503 42399M_(w) (g/mol) 104966 107517 111582 110940 M_(z) (g/mol) 251646 230247278862 237733 M_(w)/M_(n) 3.66 2.51 2.82 2.62 M_(z)/M_(w) 2.40 2.14 2.502.14 CDBI₅₀ (%) 51.4 59.7 51.9 24.5 FTIR CoMo (mol %) 2.9 3.6 2.5 2.8FTIR Branch Freq (CH₃/1000 C.) 14.5 18.1 12.7 14.1 Unsat. lnternal/100C. 0.009 0.008 0.004 0.004 Unsat. Side Chain/100 C. 0.005 0.003 0.0030.002 Unsat. Terminal/100 C. 0.048 0.029 0.03 0.021 Hexane Extractables,Plaque (%) 0.72 n/a n/a 0.42 Ti (ppm), N.A.A. 7.4 7.6 n/a 2.2 Al (ppm),N.A.A. 97.0 104 n/a 11.3 Mg (ppm), N.A.A. 85.8 90.1 n/a 14.6 Cl (ppm),N.A.A. 180 190 n/a 48.8

TABLE 12 3D-CFC characterization of Example 5 and Non-Comonomer Index.Elution SCB^(f) 3D-CFC Temp M_(w) × 10⁻⁵ M_(v) × 10⁻⁵ Avg. [n] (CH₃/1000Fraction (° C.) (wt.fr.)^(f) (g/mol) (g/mol) (dL/g) T^(f) (° C.) NCI^(f)C) F1 30-60 0.1373 0.441 0.382 0.69 52.06 0.985 28.60 F2 60-65 0.06770.660 0.596 0.99 62.66 0.990 21.46 F3 65-69 0.0793 0.832 0.767 1.2167.18 0.986 18.41 F4 69-71 0.0533 1.033 0.959 1.44 70.08 0.988 16.46 F571-73 0.0992 1.406 1.321 1.84 72.10 0.992 15.10 F6 73-74 0.0465 1.5871.499 2.03 73.51 0.988 14.15 F7 74-75 0.0800 1.736 1.655 2.19 74.500.993 13.48 F8 75-76 0.0767 1.621 1.537 2.07 75.48 0.986 12.82 F9 76-780.1218 1.308 1.220 1.75 76.92 0.982 11.85 F10 78-88 0.1551 1.036 0.9241.39 81.49 0.935  8.77 F11 88-140 0.0831 1.506 1.322 1.75 91.91 0.873 1.75

TABLE 13 3D-CFC characterization of Example 6 and Non-Comonomer Index.Elution SCB^(f) 3D-CFC Temp M_(w) × 10⁻⁵ M_(v) × 10⁻⁵ Avg. [n] (CH₃/1000Fraction (° C.) (wt.fr.)^(f) (g/mol) (g/mol) (dL/g) T^(f) (° C.) NCI^(f)C) F1 30-51 0.0993 0.618 0.564 0.88 44.95 0.983 33.39 F2 51-56 0.09040.894 0.858 1.23 53.82 0.982 27.41 F3 56-59 0.0855 1.058 1.020 1.4357.59 0.987 24.87 F4 59-61 0.0680 1.118 1.139 1.56 60.01 0.984 23.24 F561-63 0.0858 1.276 1.232 1.66 61.96 0.983 21.93 F6 63-65 0.0637 1.1981.147 1.58 63.95 0.978 20.59 F7 65-70 0.1094 1.062 0.996 1.44 67.360.974 18.29 F8 70-78 0.1375 1.172 1.064 1.49 74.00 0.931 13.82 F9 78-880.1109 1.296 1.141 1.62 82.17 0.931  8.31 F10 88-94 0.0765 1.765 1.5542.07 90.95 0.920  2.40 F11 94-140 0.0729 2.107 1.902 2.45 94.51 0.931 0.00

TABLE 14 3D-CFC characterization of Example 7 and Non-Comonomer Index.Elution SCB^(f) 3D-CFC Temp M_(w) × 10⁻⁵ M_(v) × 10⁻⁵ Avg. [n] (CH₃/1000Fraction (° C.) (wt.fr.)^(f) (g/mol) (g/mol) (dL/g) T^(f) (° C.) NCI^(f)C) F1 30-60 0.1188 0.730 0.674 1.05 53.82 0.994 27.41 F2 60-64 0.09771.078 1.041 1.49 62.23 0.994 21.75 F3 64-67 0.1226 1.290 1.255 1.7265.54 0.991 19.52 F4 67-70 0.1085 1.265 1.222 1.71 68.40 0.989 17.59 F570-75 0.1024 1.055 0.985 1.48 72.33 0.985 14.94 F6 75-80 0.1031 1.0160.928 1.45 77.66 0.988 11.35 F7 80-85 0.1138 1.135 1.030 1.56 82.400.967  8.16 F8 85-90 0.0555 1.269 1.122 1.66 87.22 0.945  4.91 F9 90-930.0505 1.538 1.369 1.94 91.88 0.936  1.77 F10 93-140 0.1272 1.813 1.6412.23 94.24 0.944  0.18

TABLE 15 3D-CFC characterization of Comparative 6 and Non-ComonomerIndex. Elution SCB^(f) 3D-CFC Temp M_(w) × 10⁻⁵ M_(v) × 10⁻⁵ Avg. [n](CH₃/1000 Fraction (° C.) (wt.fr.)^(f) (g/mol) (g/mol) (dL/g) T^(f) (°C.) NCI^(f) C) F1 30-55 0.1268 0.974 0.911 1.22 48.47 0.950 31.02 F255-58 0.0713 1.708 1.640 1.94 56.66 0.954 25.50 F3 58-60 0.0779 2.0041.940 2.19 59.09 0.940 23.86 F4 60-62 0.1005 2.082 2.015 2.26 60.980.941 22.59 F5 62-68 0.0800 1.504 1.381 1.77 63.86 0.953 20.65 F6 68-800.1170 0.525 0.466 0.85 75.21 0.958 13.00 F7 80-90 0.1743 0.639 0.5861.04 84.97 0.955  6.43 F8 90-94 0.1138 0.860 0.785 1.30 92.54 0.944 1.33 F9 94-110 0.1385 1.098 1.034 1.59 94.51 0.939  0.0

TABLE 16 Physical and molecular characteristics of Examples 10 and 11;relative to Comparatives 7 and 8. Resin Code Example 10 Example 11Comparative 7 Comparative 8 Comonomer 1-octene 1-octene 1-octene1-octene Density (g/cm³) 0.9170 0.9177 0.9045 0.9069 I₂ (dg/min) 0.700.92 0.93 1.12 S.Ex. 1.40 1.38 1.58 1.52 MFR 34.7 29.7 57.0 43.5 M_(n)(g/mol) 35536 41838 27546 36041 M_(w) (g/mol) 106261 93315 91509 90425M_(z) (g/mol) 217647 161131 246101 220700 M_(w)/M_(n) 2.99 2.99 3.322.51 M_(z)/M_(w) 2.05 1.73 2.69 2.44 CDBI₅₀ (%) 49.8 57.0 89.3 92.4 FTIRCoMo (mol %) 3.3 4.0 4.7 4.2 FTIR Branch Freq 16.7 19.8 23.4 20.9(CH₃/1000 C.) Unsat. lnternal/100 C. 0.004 0.005 0.011 0.011 Unsat. Side0.001 0.004 0.006 0.006 Chain/100 C. Unsat. 0.025 0.025 0.008 0.007Terminal/100 C. Hexane 0.21 0.41 n/a n/a Extractables, Plaque (%) Ti(ppm), N.A.A. 8.45 4.24 n/d n.d. Al (ppm), N.A.A. 187 160 — — Mg (ppm),N.A.A. 389 327 — — Cl (ppm), N.A.A. 120 69.5 — — Hf (ppm), N.A.A. 0.500.54 1.76 1.98

TABLE 17 3D-CFC characterization of Example 10 and Non-Comonomer Index.Elution SCB^(f) 3D-CFC Temp M_(w) × 10⁻⁵ M_(v) × 10⁻⁵ Avg. [n] (CH₃/1000Fraction (° C.) (wt.fr.)^(f) (g/mol) (g/mol) (dL/g) T^(f) (° C.) NCI^(f)C) F1 30-50 0.0812 0.983 0.932 1.23 44.64 0.961 33.60 F2 50-54 0.09571.582 1.532 1.81 52.27 0.955 28.46 F3 54-56 0.0666 1.884 1.835 2.1055.09 0.955 26.56 F4 56-58 0.1395 1.991 1.944 2.22 57.05 0.963 25.24 F558-60 0.1096 1.988 1.934 2.21 58.93 0.954 23.97 F6 60-68 0.0582 1.4671.346 1.70 61.96 0.943 21.93 F7 68-80 0.0777 0.364 0.314 0.64 75.670.955 12.69 F8 80-90 0.2018 0.564 0.499 0.89 85.34 0.915  6.18 F9 90-1100.1696 1.044 0.892 1.23 93.01 0.814  1.01

TABLE 18 3D-CFC characterization of Example 11 and Non-Comonomer Index.Elution SCB^(f) 3D-CFC Temp M_(w) × 10⁻⁵ M_(v) × 10⁻⁵ Avg. [n] (CH₃/1000Fraction (° C.) (wt.fr.)^(f) (g/mol) (g/mol) (dL/g) T^(f) (° C.) NCI^(f)C) F1 30-45 0.1250 0.705 0.680 0.94 40.78 0.943 36.20 F2 45-50 0.15811.156 1.128 1.41 47.83 0.944 31.45 F3 50-53 0.1496 1.368 1.341 1.6151.60 0.937 28.91 F4 53-55 0.1028 1.431 1.397 1.67 53.99 0.931 27.30 F555-62 0.1044 1.357 1.321 1.62 56.60 0.929 25.54 F6 62-94 0.0586 0.2710.203 0.49 86.11 0.962  5.66 F7 94-97 0.0938 0.565 0.504 0.97 94.510.955  0.0 F8 97-110 0.2078 1.209 1.114 1.71 98.00 0.957  0.0

TABLE 19a Reference resins (linear ethylene interpolymers) havingundetectable levels of Long Chain Branching (LCB). Reference Mv [η] SCBDResins (g/mole) (dL/g) M_(w)/M_(n) A CH₃#/1000C ZSV (poise) Resin 11.06E+05 1.672 2.14 1.9772 10.5 7.81E+04 Resin 2 1.11E+05 1.687 2.001.9772 11.2 7.94E+04 Resin 3 1.06E+05 1.603 1.94 1.9772 15.9 7.28E+04Resin 4 1.07E+05 1.681 1.91 1.9772 11.0 8.23E+04 Resin 5 7.00E+04 1.1922.11 1.9772 13.7 1.66E+04 Resin 6 9.59E+04 1.497 1.88 1.9772 12.65.73E+04 Resin 7 1.04E+05 1.592 1.85 1.9772 12.8 6.60E+04 Resin 85.09E+04 0.981 2.72 2.1626 0.0 6.42E+03 Resin 9 5.27E+04 0.964 2.812.1626 0.0 6.42E+03 Resin 10 1.06E+05 1.663 1.89 1.1398 13.3 7.69E+04Resin 11 1.10E+05 1.669 1.81 1.1398 19.3 7.31E+04 Resin 12 1.07E+051.606 1.80 1.1398 27.8 6.99E+04 Resin 13 6.66E+04 1.113 1.68 2.1626 17.81.39E+04 Resin 14 6.62E+04 1.092 1.76 2.1626 21.4 1.45E+04 Resin 156.83E+04 1.085 1.70 2.1626 25.3 1.44E+04 Resin 16 7.66E+04 1.362 2.512.1626 4.0 3.24E+04 Resin 17 6.96E+04 1.166 2.53 2.1626 13.9 2.09E+04Resin 18 6.66E+04 1.134 2.54 2.1626 13.8 1.86E+04 Resin 19 5.81E+041.079 2.44 2.1626 5.8 1.10E+04 Resin 20 7.85E+04 1.369 2.32 2.1626 3.73.34E+04 Resin 21 6.31E+04 1.181 2.26 2.1626 4.3 1.61E+04 Resin 227.08E+04 1.277 2.53 2.1626 3.6 2.58E+04 Resin 23 9.91E+04 1.539 3.092.1626 14.0 8.94E+04 Resin 24 1.16E+05 1.668 3.19 2.1626 13.3 1.32E+05Resin 25 1.12E+05 1.689 2.71 2.1626 12.8 1.38E+05 Resin 26 1.14E+051.690 3.37 2.1626 8.0 1.48E+05 Resin 28 1.00E+05 1.547 3.33 2.1626 14.19.61E+04 Resin 30 1.04E+05 1.525 3.73 2.1626 13.4 1.10E+05 Resin 311.10E+05 1.669 3.38 2.1626 8.7 1.26E+05 Resin 32 1.09E+05 1.539 3.422.1626 13.4 1.07E+05 Resin 33 8.04E+04 1.474 5.29 2.1626 1.7 7.60E+04Resin 34 8.12E+04 1.410 7.64 2.1626 0.9 9.11E+04 Resin 35 7.56E+04 1.3499.23 2.1626 1.0 9.62E+04 Resin 36 7.34E+04 1.339 8.95 2.1626 1.11.00E+05 Resin 37 1.01E+05 1.527 3.76 2.1626 13.3 1.11E+05

TABLE 19b Reference resins (linear ethylene interpolymers) havingundetectable levels of Long Chain Branching (LCB) Reference Log ZSV_(c)Log IV_(c) S_(h) S_(v) LCBF Resins (log(poise)) log(dL/g)(dimensionless) (dimensionless) (dimensionless) Resin 1 4.87E+002.46E−01 −5.77E−02 −1.21E−02 3.49E−04 Resin 2 4.90E+00 2.52E−01−5.39E−02 −1.13E−02 3.05E−04 Resin 3 4.87E+00 2.41E−01 −2.46E−02−5.16E−03 6.33E−05 Resin 4 4.93E+00 2.50E−01 −9.46E−03 −1.99E−039.41E−06 Resin 5 4.20E+00 1.07E−01 −6.37E−02 −1.34E−02 4.26E−04 Resin 64.78E+00 2.04E−01 5.83E−02 1.22E−02 3.57E−04 Resin 7 4.85E+00 2.31E−01−1.73E−03 −3.65E−04 3.16E−07 Resin 8 3.69E+00 −8.43E−03 −2.17E−02−4.55E−03 4.93E−05 Resin 9 3.68E+00 −1.58E−02 1.21E−04 2.44E−05 1.47E−09Resin 10 4.91E+00 2.38E−01 2.19E−02 4.60E−03 5.04E−05 Resin 11 4.90E+002.48E−01 −2.96E−02 −6.21E−03 9.17E−05 Resin 12 4.88E+00 2.42E−01−1.99E−02 −4.19E−03 4.17E−05 Resin 13 4.21E+00 9.14E−02 2.36E−024.96E−03 5.86E−05 Resin 14 4.21E+00 9.22E−02 1.89E−02 3.97E−03 3.75E−05Resin 15 4.22E+00 1.00E−01 −9.82E−03 −2.06E−03 1.01E−05 Resin 164.42E+00 1.44E−01 −1.23E−02 −2.59E−03 1.60E−05 Resin 17 4.23E+001.01E−01 −4.64E−03 −9.75E−04 2.26E−06 Resin 18 4.18E+00 8.91E−021.66E−03 3.47E−04 2.87E−07 Resin 19 3.97E+00 4.73E−02 −1.09E−02−2.29E−03 1.25E−05 Resin 20 4.47E+00 1.45E−01 2.28E−02 4.78E−03 5.44E−05Resin 21 4.16E+00 8.23E−02 1.78E−02 3.73E−03 3.31E−05 Resin 22 4.32E+001.15E−01 2.45E−02 5.14E−03 6.30E−05 Resin 23 4.78E+00 2.22E−01 −2.25E−02−4.73E−03 5.31E−05 Resin 24 4.94E+00 2.56E−01 −3.13E−02 −6.57E−031.03E−04 Resin 25 5.02E+00 2.59E−01 3.91E−02 8.21E−03 1.60E−04 Resin 264.97E+00 2.48E−01 3.94E−02 8.27E−03 1.63E−04 Resin 28 4.79E+00 2.24E−01−3.13E−02 −6.57E−03 1.03E−04 Resin 30 4.80E+00 2.18E−01 1.47E−023.08E−03 2.26E−05 Resin 31 4.90E+00 2.44E−01 −1.40E−02 −2.94E−032.06E−05 Resin 32 4.82E+00 2.23E−01 1.27E−02 2.66E−03 1.69E−05 Resin 334.51E+00 1.72E−01 −6.37E−02 −1.34E−02 4.26E−04 Resin 34 4.45E+001.52E−01 −2.68E−02 −5.62E−03 7.52E−05 Resin 35 4.40E+00 1.33E−011.55E−02 3.26E−03 2.53E−05 Resin 36 4.43E+00 1.30E−01 5.82E−02 1.22E−023.55E−04 Resin 37 4.80E+00 2.17E−01 1.77E−02 3.71E−03 3.28E−05

TABLE 20 Long Chain Branching Factor (LCBF) of ethylene/1-octeneinterpolymers: Examples 1, 4-7, 10 and 11. Example Example ExampleExample Example Example Example Sample 1 4 5 6 7 10 11 M_(V) (g/mole)109000 104000 101000 111000 109000 104000 102000 [η] (dL/g) 1.570 1.5311.497 1.565 1.600 1.433 1.410 M_(w)/M_(n) 3.61 3.80 3.77 2.51 3.18 2.992.23 A 2.1626 2.1626 2.1626 2.1626 2.1626 2.1626 2.1626 SCB (CH₃#/1000C)13.5 13.7 14.5 18.1 12.7 16.7 19.8 ZSV (poise) 107000 106000 857000103000 107000 247000 158000 Log ZSV_(c) (log(poise)) 4.80 4.78 4.69 4.934.85 5.24 5.16 Log IVc (log(dL/g)) 0.231 0.220 0.212 0.241 0.236 0.2020.202 S_(h) (dimension-less) −0.0487 −0.0202 −0.0721 0.0250 −0.02400.527 0.442 S_(v) (dimension-less) −0.0102 −0.0042 −0.0152 0.00526−0.00505 0.111 0.00929 LCBF (dimension-less) 2.49E−04 4.28E−05 5.47E−046.58E−05 6.06E−05 0.0291 0.0205

TABLE 21 Long Chain Branching Factor (LCBF) of ethylene/1-octeneinterpolymers: Comparatives 1 and 3-8. Sample Comp. 1 Comp 3 Comp 4 Comp5 Comp 6 Comp 7 Comp 8 M_(v) (g/mole) 102000 94200 87900 88000 10400091100 86500 [η] (dL/g) 1.553 1.474 1.300 1.284 1.507 1.286 1.245M_(w)/M_(n) 3.80 3.08 1.88 1.87 2.79 3.32 2.51 A 2.1626 2.1626 2.16262.1626 2.1626 2.1626 2.1626 SCB (CH₃#/1000C) 13.2 14.6 23.2 22.3 14.123.4 20.9 ZSV (poise) 118000 89790 151000 180000 155000 257000 190000Log ZSV_(c) (log(poise)) 4.83 4.79 5.20 5.28 5.06 5.22 5.19 Log IVc(log(dL/g)) 0.224 0.205 0.174 0.167 0.215 0.172 0.151 S_(h)(dimensionless) 0.00830 0.0617 0.622 0.732 0.290 0.646 0.718 S_(v)(dimensionless) 0.00174 0.0130 0.131 0.1054 0.0609 0.136 0.151 LCBF(dimensionless) 7.23E−6 4.00E−4 0.0406 0.0563 0.00883 0.0438 0.0541

TABLE 22 Blown film manufacturing conditions Examples 1 and 3 andComparative 2. Resin Code Example 2 Example 3 Example 3 Comp. 2 Comp. 2Film Thickness (mil) 1 2 4 2 4 Output (lb/hr) 40.0 40.2 67.5 40.6 62.0Die Gap (mil) 35 35 35 35 35 BUR 2.5:1 2.5:1 2.5:1 2.5:1 2.5:1 BarrelZone 1 (° F.) 420 417 418 422 418 Barrel Zone 2 (° F.) 400 400 401 400400 Barrel Zone 3 (° F.) 400 400 400 400 400 Adapter Zone 4 (° F.) 400400 400 400 400 Die Body Zone 5 (° F.) 420 420 420 420 420 Die Body Zone6 (° F.) 420 420 427 429 437 Die Lip Zone 7 (° F.) 440 440 440 440 440Melt Temperature (° F.) 438 433 469 447 479 Current (Amp) 32.0 34.0 41.134.0 41.0 Voltage (V) 140 139 235 140 235 Pressure High (psi) 2835 26203310 3030 3700 Pressure Low (psi) 2755 2510 3250 2920 3650 Avg. Pressure(psi) 2795 2565 3280 2975 3675 Screw Speed (rpm) 87.8 87.5 157.4 88.9157.5 Air Temperature (° F.) 51 48 50 n/a 49 Frostline Height (inch) 7.08.25 17 9.0 16.5 Line Speed (ft/min) 71.7 35.4 30.0 35.5 30.0 Screw Typemaddox maddox maddox maddox maddox Specific Output (lb/hr/rpm) 0.46 0.460.43 0.46 0.39 Specific Power ((lb/hr)/amp) 1.25 0.12 1.64 1.19 1.51Specific Energy (W/lb/hr) 112.0 117.6 143.1 117.2 155.40

TABLE 23 Blown film physical properties Examples 1 and 3 and Comparative2. Sample Code Example 2 Example 3 Example 3 Comp. 2 Comp. 2 Density(g/cm³) 0.9208 0.9200 0.9200 0.9182 0.9208 I₂ (dg/min) 1.02 0.96 0.960.98 0.97 Thickness (mil) 1.00 2.04 3.99 2.07 3.65 Dart Impact, F₅₀ (g)325 365 256 175 150 Tear - MD (g/mil) 318 370 491 438 429 Tear - TD(g/mil) 638 558 604 646 729 Tensile Strength @ Break 55.4 51.4 48.8 49.445.8 MD (MPa) Tensile Strength @ Break TD 55.7 51.6 44 45 45.4 (MPa)Tensile Yield Strength - MD 10.2 10.6 10.8 11.6 11.5 (MPa) Tensile YieldStrength - TD (MPa) 10.5 10.8 11.1 11.8 12 Tensile Elongation MD (%) @555 603 714 699 745 Break MD (MPa) Tensile Elongation TD (%) @ 827 716717 696 743 Break MD (MPa) Tensile Elongation @ Yield MD 16 14 16 15 17(%) Tensile Elongation @ Yield TD 24 19 17 14 12 (%) Tensile Energy (J)MD 1.96 1.84 4.02 2.27 4.04 Tensile Energy (J) TD 2.55 2.22 3.69 2.013.88 1% Secant Modulus MD (MPa) 193 185 185 203 215 1% Secant Modulus TD(MPa) 224 213 214 241 259 2% Sec. Modulus MD (MPa) 163 160 161 174 1842% Sec. Modulus TD (MPa) 184 176 182 199 213 Film Haze (%) 5 8 13 7 12Film Gloss @ 45° 78 69 69 73 73 Hot Tack Strength (N) n/a 5.70 5.61 4.585.07 Hot Tack Onset @0.5 N (° C.) n/a 87.0 86.9 87.0 90.3 Hot Tack Onset@1.0 N (° C.) n/a 90.5 90.3 92.0 91.7 Heat Seal Temperature @ Max. n/a125 110 130 110 Heat Seal Strength (° C.) Film Hexane Extractables (3.5mil n/a n/a 0.76 n/a 0.70 film)

TABLE 24 Blown film physical properties Example 6 relative toComparative 9; 1.0 mil monolayer film. Sample Code Example 6 Comparative9 Density (g/cm³) 0.919 0.919 I₂ (dg/min) 0.85 0.85 Tear - MD (g/mil)305 275 Tear - TD (g/mil) 589 470 Dart Impact, F₅₀ (g) 824 475 TensileStrength @ Break MD (MPa) 56 49 Tensile Strength @ Break TD (MPa) 47 40Tensile Yield Strength - MD (MPa) 9.5 9.5 Tensile Yield Strength - TD(MPa) 9.3 9.8 Tensile Elongation MD (%) @ Break 572 520 MD (MPa) TensileElongation TD (%) @ Break 715 700 MD (MPa) 1% Secant Modulus MD (MPa)159 165 1% Secant Modulus TD (MPa) 167 175 Film Haze (%) 11 22 FilmGloss 45° 73 35

1. An ethylene interpolymer product comprising: (i) a first ethyleneinterpolymer; (ii) a second ethylene interpolymer, and; (iii) optionallya third ethylene interpolymer; wherein said second ethylene interpolymeris characterized by an intermediate branching, wherein said intermediatebranching is characterized by a Non-Comonomer Index Distribution,NCID_(i), having a value characterized by Eq. (1a) and Eq. (1b);NCID_(i)≤1.000−0.00201(log M _(i)−log M _(o)+4.93)+0.00137(log M_(i)−log M _(o)+4.93)²−0.00034(log M _(i)−log M _(o)+4.93)³  Eq.(1a)NCID_(i)≥0.730−0.00388(log M _(i)−log M _(o)+4.93)+0.00313(log M_(i)−log M _(o)+4.93)²−0.00069(log M _(i)−log M _(o)+4.93)³  Eq.(1b)wherein, M_(o) is a peak molecular weight that characterizes a molecularweight distribution of said second ethylene interpolymer when fit to alog normal distribution and M_(i) is an incremental molar mass thatcharacterizes said molecular weight distribution; wherein a firstderivative of said NCID_(i), $\frac{{dNCID}_{i}}{d\log M_{i}},$  Eq.(2), $\begin{matrix}{\frac{{dNCID}_{i}}{d\log M_{i}} = {\beta_{1} + {2{\beta_{2}\left( {{\log M_{i}} - {\log M_{o}} + 4.93} \right)}} + {3{\beta_{3}\left( {{\log M_{i}} - {\log M_{o}} + 4.93} \right)}^{2}}}} & {{Eq}.(2)}\end{matrix}$ has a value of ≤−0.0001, coefficients β₀, β₁, β₂ and β₃are generated by fitting said NCID_(i) of said second ethyleneinterpolymer to a third order polynomial, Eq. (3),NCID_(i)=β₀+β₁(log M _(i)−log M _(o)+4.93)+β₂(log M _(i)−log M_(o)+4.93)²+β₃(log M _(i)−log M _(o)+4.93)³  Eq.(3) wherein saidNCID_(i) of said second ethylene interpolymer is obtained bydeconvoluting an experimentally measured Non-Comonomer IndexDistribution of said ethylene interpolymer product; wherein saidethylene interpolymer product contains long chain branching ascharacterized by a dimensionless Long Chain Branching Factor, LCBF,having a value of >0.001.
 2. The ethylene interpolymer product of claim1, wherein said first ethylene interpolymer is synthesized using ahomogenous catalyst formulation and said second ethylene interpolymer issynthesized using an intermediate branching catalyst formulation.
 3. Theethylene interpolymer product of claim 2, wherein said homogeneouscatalyst formulation is a bridged single site catalyst formulation andsaid intermediate branching catalyst formulation is an in-lineintermediate branching catalyst formulation or a batch intermediatebranching catalyst formulation.
 4. The ethylene interpolymer product ofclaim 1 having a melt index from about 0.3 to about 500 dg/minute and adensity from about 0.858 to about 0.965 g/cc; wherein melt index ismeasured according to ASTM D1238 (2.16 kg load and 190° C.) and densityis measured according to ASTM D792.
 5. The ethylene interpolymer productof claim 1 having a M_(w)/M_(n) from about 2 to about
 25. 6. Theethylene interpolymer product of claim 1 having a CDBI₅₀ from about 10%to about 98%; wherein CDBI₅₀ is defined as the percent of said ethyleneinterpolymer product having a comonomer composition within 50% of themedian comonomer composition as determined by CTREF.
 7. The ethyleneinterpolymer product of claim 1; wherein (i) said first ethyleneinterpolymer has a melt index from about 0.001 to about 1000 dg/minute,a density from about 0.855 g/cm³ to about 0.975 g/cc and is from about 0to 60 weight percent of said ethylene interpolymer product; (ii) saidsecond ethylene interpolymer has melt index from about 0.001 to about1000 dg/minute, a density from about 0.89 g/cm³ to about 0.965 g/cc andis from about to 99 weight percent of said ethylene interpolymerproduct; (iii) optionally said third ethylene interpolymer has a meltindex from about 0.1 to about 10000 dg/minute, a density from about0.855 to about 0.975 g/cc and is from 0 to about 30 weight percent ofsaid ethylene interpolymer product; wherein melt index is measuredaccording to ASTM D1238 (2.16 kg load and 190° C.), density is measuredaccording to ASTM D792 and weight percent is the weight of said first,said second or said optional third ethylene interpolymer divided by theweight of said ethylene interpolymer product.
 8. The ethyleneinterpolymer product of claim 1 synthesized using a solutionpolymerization process.
 9. The ethylene interpolymer product of claim 1further comprising from 0.001 to about 10 mole percent of one or moreα-olefin.
 10. The ethylene interpolymer product of claim 9; wherein saidone or more α-olefin are C₃ to C₁₀ α-olefins.
 11. The ethyleneinterpolymer product of claim 10; wherein said one or more α-olefin is1-hexene, 1-octene or a mixture of 1-hexene and 1-octene.
 12. Theethylene interpolymer product of claim 1 wherein said third ethyleneinterpolymer is synthesized using a heterogeneous catalyst formulationor a homogeneous catalyst formulation or an intermediate branchingcatalyst formulation.
 13. The ethylene interpolymer product of claim 1;wherein said first ethylene interpolymer has a first CDBI₅₀ from about20 to about 98%, said second ethylene interpolymer has a second CDBI₅₀from about 20 to about 70% and said optional third ethylene interpolymerhas a third CDBI₅₀ from about 20 to about 98%.
 14. The ethyleneinterpolymer product of claim 13; wherein said first CDBI₅₀ is higherthan said second CDBI₅₀.